Viktor Troicki will open the first round for Serbia against Karen Kachanov before Novak faces Daniil Medvedev on Day 1.
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.
The world’s biggest indoor tournament begins on Sunday, November 13, at the O2 Arena in London.
Novak is a top seed and will open his campaign in singles competition against world no.145, Juan Martin del Potro (ARG).