Following her first round win over Venus Williams, British star Laura Robson has an almost immediate return to action as she hopes to build on her surprise win.
However, standing in her way and looking to avenge her sister's defeat will be world No.1 Serena Williams, who arrives in the Italian capital after lifting her 50th career singles title in Madrid on Sunday.
The pair have never met before, and while Serena revealed it will be "a tough second round", it is difficult to envisage her being put under too much pressure considering her current form.
There is undoubtedly value to be had elsewhere though, with No.12 seed Maria Kirilenko getting her tournament underway against Spanish qualifier Anabel Medina Garrigues.
The Russian ace has won their last two meetings, but both have gone the distance including a round of 32 clash at the Foro Italico back in 2008. Kirilenko has arguably come on leaps and bounds since in comparison to her opponent, and should be backed to prevail but could face a tough test.
Madrid semi-finalist Ana Ivanovic is also in action on Tuesday, as she looks to maintain what has been an impressive run of form this year thus far. She takes on Urszula Radwanska in her first round match, while Agnieszka Radwanska faces qualifier Simona Halep.
Elsewhere, there is an all-Belgian clash taking place as compatriots Yanina Wickmayer and Kirsten Flipkens prepare to face off. Despite her inferior world ranking, Wickmayer appears to have the better of her countrywoman given her 3-0 record in previous meetings and could be worth a look as a result.
Caroline Wozniacki also joins the party on Tuesday but has had a disappointing year by her high standards, and will be hoping to make an impression in Rome with less than two weeks to go until the French Open.
She kicks things off for the women's side of the draw on Tuesday morning when she takes on Serbian world No. 48 Bojana Jovanovski, and will certainly be focused on getting off to a strong start.
Meanwhile, world No.3 Victoria Azarenka will have a keen eye on proceedings out on Court 6 as she awaits the winner of Julia Goerges' meeting with Andrea Hlavackova. The latter has had a miserable year to date, so expect the German to wrap up an imposing victory.
There is potential for further upsets on Tuesday, not least in the second round clash between Petra Kvitova and Sabine Lisicki. The German ace brushed aside qualifier Mallory Burdette in the opening round, and has both the precision and skill to trouble her rival.