British No 1 Laura Robson will meet Venus Williams in the first round in Rome next week - and then Serena Williams if she wins.
With 19-year-old Robson up against Venus in round one, Venus' sister, world number one Serena, who has a first-round bye, awaits the winner.
The draw is something of a setback for Robson's hopes of being seeded at the forthcoming French Open.
She boosted her chances by reaching the third round in Madrid this week - a run which will see her return to the world's top 40 on Monday - but she is likely to have to beat both Williams sisters if she is to earn a seeding.
The highest 32 ranked players in the draw will be seeded at Roland Garros.
Robson, who split from coach Zeljko Krajan recently and will work with former British professional Lucie Ahl in Rome.
As top seed, Serena is scheduled to face Angelique Kerber in the last eight before playing the winner of the projected Agnieszka Radwanska-Li Na quarter-final in the semis.
On the other side of the draw, defending champion Maria Sharapova is seeded to meet Sara Errani in the quarter-finals.
The match would be a repeat of their French Open final of last season. A clash with Victoria Azarenka could follow.
The action gets under way in the Italian capital on Monday.