She hit a 124.9 mph (201.0 km/h) serve at the French Open in 2007, the fifth fastest serve of all time on the WTA Tour. However, from 2009 to 2012, her service game has largely been viewed as a liability instead of a weapon. This is because of her inconsistent ball tosses which are directly associated with her diminishing confidence. Nonetheless, in 2013, under the tutelage of Nigel Sears, her ball tosses become more consistent, allowing her to build her game on her powerful first serves.
The pair first met in the second round of the 2005 NASDAQ-100 Open with Ivanovic winning in straight sets. Later in the year, Petrova reached the semifinals of the French Open by defeating Ivanovic in straight sets in the quarterfinals. In the next two matches both players won one, and both were in a round of 16. Ivanovic won two significant matches in 2007. First, she beat Petrova in the 4th round of Wimbledon after a rollercoaster three set match. Later in the summer Ivanovic won in straight sets in their only meeting in a final, in Los Angeles. At that time, it was 4–2 for Ivanovic in their head-to-head, but Petrova won the next two meetings in two close matches to level the result. However, Ivanovic won five of the next six meetings, including the quarterfinals of the 2010 Internazionali BNL d'Italia when Petrova retired but after Ivanovic had won the first nine games, and the semifinals of the 2011 Commonwealth Bank Tournament of Champions in Bali, which Ivanovic won in straight sets.
Aside from her tennis career, she also studies finance at a university in Belgrade, and Spanish in her spare time. On 8 September 2007, Ivanovic became a UNICEF National Ambassador for Serbia, alongside Aleksandar Đorđević, Jelena Janković, Emir Kusturica and Novak Djokovic. She takes a special interest in the fields of education and child protection. Ivanovic visited a primary school in Serbia during her inauguration and said that she is "also looking forward to going into the classroom and meeting many kids".
Ivanovic has appeared as a character in Smash Court Tennis 3, released in 2007, Virtua Tennis 2009, released in 2009, Grand Slam Tennis for Wii, also released in 2009, Top Spin 4 and Virtua Tennis 4 both released in 2011. She is also featured in Grand Slam Tennis 2, released in 2012. She stars, among others, alongside Novak Djokovic, Roger Federer, Rafael Nadal, Lindsay Davenport, Anna Chakvetadze, Venus Williams and Maria Sharapova.