1 Serena Williams in the semifinals to end her hopes of achieving the Grand Slam, in what has been described by commentators as one of the greatest upsets in tennis history.

[11] Vinci qualified for the Brisbane International and defeated Anna-Lena Grönefeld in the first round, before losing to top seed Ana Ivanovic in the second.

At her first clay-court event, Mexican Open in Acapulco, Vinci defeated sixth seed Lucie Šafářová in the first round, and then fell to Ágnes Szávay of Hungary.

At the Barcelona Open, Vinci earned her second career title, defeating Pauline Parmentier in the first round, Flavia Pennetta in the second, Anastasiya Yakimova in the quarterfinals, Francesca Schiavone in the semifinals, and defending champion Maria Kirilenko in the final.

Roberta then suffered early round losses at the Apia International Sydney and the Australian Open to Daniela Hantuchová and Zheng Jie, respectively.

She defeated Simona Halep 6–4, 6–4, then Bethanie Mattek-Sands 6–3, 1–6, 6–3, before falling to eventual finalist Marion Bartoli in a third-set tiebreaker in the quarterfinals.

Seeded first in both events, she was upset by Nina Bratchikova in the second round of Monterrey, before bowing out to eventual champion Sara Errani in the semifinals at Acapulco.

Vinci and Errani managed to win the doubles title of the Barcelona Open by beating Francesca Schiavone and Flavia Pennetta in an all-Italian final, with the score of 6–2, 6–0.

[14] At the Canadian Open in Montreal, Vinci defeated Yanina Wickmayer 6–2, 3–6, 7–5, after coming back from a 1–5 and match point deficit in the third set.

After she defeated the 6th seed Angelique Kerber with the result of 6–2, 7–6, but she was beaten in the quarterfinals by the Czech Lucie Šafářová in straight sets.

Two weeks later Vinci defeated Jelena Janković 7–5, 6–3 to win her seventh WTA title at the Texas Tennis Open without losing a set in the entire tournament.

Vinci won her eighth WTA title when defeated top-seeded Petra Kvitová, 7–6, 6–1, to win the Katowice Open in Poland.

After that, Vinci competed at Internazionali di Palermo and won her 9th title by defeating doubles partner Sara Errani in the final.

Vinci and Errani once again qualified for the Tour Championships but lost in the semifinals again to a Russian pair, Ekaterina Makarova and Elena Vesnina.

Vinci faced Petra Kvitová during Italy's semifinal Fed Cup tie against Czech team but lost in straight sets.

At the US Open, Vinci won her first Grand Slam singles match of 2014 by defeating Paula Ormaechea in the first round followed by a three-set win over Irina-Camelia Begu.

At the Luxembourg Open, Vinci the sixth seed easily defeated Tereza Smitková in the first round but then lost to Beck in straight sets.

[19] At the Australian Open, Vinci overcame Bojana Jovanovski to reach round two but lost to tenth seed Ekaterina Makarova, 2–6, 4–6.

[24] Beginning her clay-court season seeded sixth at the Morocco Open, Vinci lost to fellow Italian Karin Knapp in the second round, 7–6, 2–6, 2–6.

[33] Last year finalist at the İstanbul Cup, Vinci reached the quarterfinals beating seventh seed Anastasia Pavlyuchenkova and qualifier Alexandra Panova.

[34] Vinci then reached her second quarterfinal at the Canadian Open by defeating Karin Knapp, qualifier Mirjana Lučić-Baroni, and Daria Gavrilova all in straight sets.

[38] Ranked 43 at the US Open, Vinci won her first three rounds defeating Vania King, Denisa Allertová, and Mariana Duque Mariño.

Vinci then reached her third US Open quarterfinal in four years after Eugenie Bouchard withdrew a few hours before their fourth-round match after she slipped and hit her head in the locker room.

Numerous major media outlets reported about Vinci's win over Williams being one of the biggest upsets in tennis history.

Seeded 9th at the Qatar Total Open, Vinci defeated Lesia Tsurenko, Daria Kasatkina, and wildcard Çağla Büyükakçay to reach the quarterfinals.

[81] Seeded sixth at Wimbledon, Vinci reached the third round defeating Alison Riske and lucky loser Duan Yingying.

She reached the quarterfinals for the fourth time in five years, defeating Anna-Lena Friedsam, Christina McHale, Carina Witthöft, and Lesia Tsurenko.

[109] As the 31st seed at the French Open, Vinci was defeated in the first round by the previous year's Olympic gold medalist Monica Puig, 6–3, 3–6, 6–2.

[115] Having announced her plans to retire after the Italian Open, Vinci continued to play sporadically through the early part of the season.

[122] Due to her backhand slice, powerful forehand and excellent court covering, her game is often compared to Steffi Graf.