Rodionova has won nine singles and 29 doubles titles on the ITF Women's Circuit. In 2007, she won the Australian Open girls' doubles title, partnering Evgeniya Rodina. On 23 October 2017, she reached her career-high singles ranking of world No. 116. On 27 July 2015, she peaked at No. 41 in the doubles rankings.
Elder sister Anastasia is also a tennis professional, and the two sisters have intermittently contested doubles tournaments with modest success. Their most notable achievement as a team came at the 2010 Malaysian Open, in which they reached the final before losing to Chan Yung-jan and Zheng Jie in a super tie-break.
Arina Rodionova was born to Ivan and Natalia Rodionova and lives in Melbourne with her sister Anastasia. She began playing tennis aged three, "I began playing tennis when I was almost three years old. And why exactly tennis? There wasn't any choice for me with my dad being a coach and my sister a professional tennis player, but in the end I think it's worked well!" Rodionova cites Martina Hingis as her role model, and also admires Justine Henin and Bob and Mike Bryan. She prefers hard courts and forehand as a shot.
Rodionova made her debut as a professional in 2004 at an ITF event in Protvino, Russia. In 2005, she won a title in Minsk, followed by another win in Moscow the following year. In 2008, she finished as a runner-up in an ITF event in Istanbul. In 2009, Rodionova won two ITF titles in singles and eight in doubles.
In 2010, Rodionova defeated Jarmila Groth in the final of a $25,000 tournament in Burnie. In doubles, she advanced to the final of the WTA-level Malaysian Open with her sister Anastasia. Although they defeated No. 1 seeds Alisa Kleybanova and Yan Zi along the way, the sisters lost the final match to Chan Yung-jan and Zheng Jie in close three sets.
At the 2011 Australian Open, Rodionova equalled her career-best showing at a Grand Slam tournament by qualifying for the main draw. She lost in the first round to fellow qualifier Anne Keothavong, 5–7, 4–6. She then won a $50,000 event in May in Prague, partnering Darya Kustova. She qualified for the Aegon Classic, and won her first-round match against Virginie Razzano. She then notched the biggest win of her career by defeating No. 1 seed and world No. 16 Kaia Kanepi in the second round. She lost to the 14th seed Magdaléna Rybáriková in the third round. At Wimbledon, Rodionova barely missed out on qualifying for the main draw by losing to Kristýna Plíšková in three sets. She achieved very modest results through much of the rest of the year, losing in the first or second round of most tournaments she entered.
Rodionova in 2014
In 2012, Rodionova lost in the qualifying rounds of the Apia International Sydney and the Australian Open. She then lost in the quarterfinals of a $25,000 event in Burnie. She then competed in two more ITF events – losing in the second and first round, respectively. She picked up form in ITF Mildura, reaching the semifinals. Rodionova then competed in three more tournaments, losing in the second round of all three. She then failed to qualify in Copenhagen. Her best result of the year came at the WTA clay event Grand Prix SAR La Princesse Lalla Meryem. She defeated Darija Jurak, Karolína Plíšková, and world No. 108 Mathilde Johansson to qualify for the main draw. Each match lasted three sets. She took on Timea Bacsinszky in the first round, started well by winning the first set 6–2, but was forced to retire due a severe wrist injury she sustained while trailing 0–4 in the second set. She was also forced to withdraw from the doubles competition, where she and Anastasia were the No. 1 seeds. She missed a big part of the clay-court season to recover from the injury. Rodionova returned in July; she was only able to make it past the first round in one of five ITF tournaments. However, she had a great result in Las Vegas, where she reached the semifinals. Following three more early exits in tournaments, she reached the final of a $25,000 event in Traralgon, and followed this up by winning her next tournament in Bendigo. She finished the year with two more early-round losses in Toyota and Dubai.
In 2011, Rodionova was drafted by the Washington Kastles WTT Team, coached by Murphy Jensen. As a result of their 14-match win undefeated regular season, the Kastles secured the top seed in the Conference Championships where they beat the Boston Lobsters. In the WTT Finals the Kastles defeated the St. Louis Aces to capture the 2011 WTT Championship for the second time in its four-year existence, completing the first ever 16–0 season in WTT 36-year history. Rodionova was named Female Rookie of the Year just prior to the Conference Championship match and later WTT Finals MVP.