Training for the preseason on July 13, 2013, Sassuolo took home the TIM Trophy after losing to Juventus on penalties , before beat Milan by a score of 2-1. This was the first time that a club different from Milan, Internazionale or Juventus have been awarded the Cup.
On August 25, 2013 Sassuolo had their first Serie A match, a defeat of 2-0 away from Torino. The following match was their first home match against Livorno and Simone Zaza scored the team's first goal in the top flight as they fell 4-1. On 22 September 2013, Sassuolo endured a heavy 7-0 defeat at home to Internazionale. Sassuolo scored their first points in their fifth game, on the 25th of September, away from Napoli. Zaza scored a goal as the match ended at 1-1 and ended Napoli's flawless beginning to their season. It was followed by their first home win on the 29th of September after a draw with Lazio. 20 October 2013 was the day that Sassuolo had the initial Serie A game, defeating Bologna at home 2-1 with goals scored by Domenico Berardi and Antonio Floro Flores which lifted the club from the bottom of the table. Sassuolo defeated away at first on Serie A on 3 November against Sampdoria where Berardi scored their first top-flight goal to beat them 4-3. After the next game, a 1-1 draw against Roma on November 10 The club is not in the zone of relegation. On the 12th of January, Berardi was the only player of the season that scored 4 goals within one game in which Sassuolo was able to come back from two goals down to beat Milan 4-3. Milan. In the final days in January 2014 Sassuolo had fallen to the bottom spot and their manager Di Francesco was relieved of his duties, and Alberto Malesani was brought in. The management change didn't have the expected outcomes, so in March, Sassuolo was able to return its team to the supervision by Di Francesco. Sassuolo had a win in an away game with Fiorentina 4-3 on May 6, 2014, and following a win of 4-2 at home against Genoa on May 11, Sassuolo guaranteed its place in Serie A for the 2014-15 season. Berardi was in 7th on the Serie A top scorers list with 16 goals in the season.
The Neroverdi experienced a far superior 2014-15 Serie A season, finishing just a few points above the relegation zone at 12th position. Berardi was once again the top goal scorer for the club with the club scoring 15 goals in league play.
Sassuolo's performance improved during the 2016-17 Serie A season, finishing ahead of of Milan and Lazio in sixth position. The league started with the opening day victory over Napoli and the Round 10 win 1-0 against Juventus at the Mapei Stadium and a 1-0 victory against Inter in the San Siro.
On the 21st of May, 2016 Sassuolo made history by achieving their first Europa League qualification after finishing sixth in the 2015-16 season thanks to an Juventus Coppa Italia win over Milan in the sense that Milan could have travelled to Europe rather than Europe if they had been victorious in the final. On the 25th of August, 2016 Sassuolo was able to qualify to play in qualifying for the Europa League group stage after defeating Red Star Belgrade 4-1 on an aggregate score in the playoff round.
The following three seasons over the next three seasons, the Neroverdi returned to mid-tablestatus, concluding the 2016-17 season 12th position. Then the club followed by achieving consecutive 11th position finish in both 2018 and in 2019 before being eliminated during the Round of 16 three consecutive Coppa Italia campaigns. In the match at home against Lazio on February 25, 2018 the captain of the club Francesco Magnanelli played his 400th game for Sassuolo since joining the club's latest season of Serie C2 in 2005, having been the captain of the Neroverdi through three promotions while also participating in European competition during that time. On June 13, 2018 Roberto De Zerbi was named manager, following being awed by his play-based approach in the being relegated Benevento during earlier seasons.
The 2019-20 season saw an improvement in the fortunes of Sassuolo. The club ended the season 8th and was just outside of the final qualification position of the UEFA Europa League, marking only the second top-half Serie A finish in its history. One of the main reasons for the growth of Sassuolo was De Zerbi's creative, attacking style of play. This has been thriving and culminated in an unprecedented Serie A goal return of 69, which is the highest number the club has seen since its it was promoted in 2013. The departure to Francesco Caputo from Empoli in the previous off-season was significant to this, as Caputo finished the season having scored 21 league goals and the wingers Jeremie Boga, and Domenico Berardi also achieved double-figure goals.
The club continued its growth as the top club within Serie A in the following season, where it was 61. from 2015-16 was broken by another 8th-place finish with the score of 62 points. After eight games Sassuolo was ranked second on the table, that was in large part due to the outstanding performance of players like Berardi, Manuel Locatelli, Filip Duricic, amongst others. A 2-0 win away over Napoli on matchday 6 is perhaps the best example of the impressive start to the season. While the team's form deteriorated little in the middle part and the final stages of their season, the 2-0 win against Lazio on the last day of play was a sign that Sassuolo had reached the same number of points as Roma in seventh place however, it was just a hair short of European qualifying on the basis of goal difference. Berardi was in his eighth season at the club, had the best season of his career. He scored 17 league goals. His double in a 3-1 victory over Fiorentina on the 17th of April in 2021 was the day he attained 100 goals in every competition with the Neroverdi. De Zerbi announced he would depart the club at close of the season to fill the vacant position of head coach in Shakhtar Donetsk. On July 11, 2021 Sassuolo's Manuel Locatelli, Domenico Berardi and Giacomo Raspadori were part of the Italy national team that beat England during the UEFA Euro 2020 final.