Defending champion Andy Murray of Britain will face Viktor Troicki in the first round of the Olympics in Rio.
Johanna Konta plays Stephanie Vogt of Liechtenstein and fellow Briton Heather Watson also faces a player outside the top 250 in Peng Shuai of China.
Kyle Edmund plays Australian Jordan Thompson, while the Murray brothers begin the doubles against Brazilian pair Thomaz Bellucci and Andre Sa.
Serbia's Novak Djokovic opens his campaign against Juan Martin Del Potro.
More to follow