Nole will play at the ATP 250 event in preparation for the only tennis Grand Slam on grass, The Championships, Wimbledon.
Novak won his first French Open title in 2016 and completed career Grand Slam beating Andy Murray in the final (3-6, 6-1, 6-2, 6-4).
The last of three ATP World Tour Masters 1000 events contested on clay takes place in the capital of Italy from May 14-21.
The 2011 and 2016 champion will open campaign at La Caja Mágica in R2 against Spanish wild card Nicolas Almagro (ATP #76).
Novak will open against Albert-Ramos-Vinolas, before Troicki plays Pablo Carreno Busta on Day 1.
Nole is no.1 seed and will open his Abierto Mexicano Telcel campaign against world no.65 Martin Klizan.
Viktor Troicki will open the first round for Serbia against Karen Kachanov before Novak faces Daniil Medvedev on Day 1.
The 12-time Grand Slam titlist headlines Serbia’s team nominations and will be joined in the line-up by Troicki, Lajovic and Zimonjic.
Second seed and six-time defending champion will open campaign in his 13th Australian Open appearance against world no.40 Fernando Verdasco.
Novak is no.2 seed and will open his title defence campaign against Jan-Lennard Struff (ATP #63). It will be their first career meeting.