Top seeded Roger Federer could meet Murray in the final in a repeat of Wimbledon earlier this month, after the pair were drawn on opposite sides of the competition.
Third seed Murray will take on Federer's fellow-Swiss Wawrinka in his opening match.
Top seeded mens duo Mike and Bob Bryan will play Brazil's Thomaz Bellucci and Andre Sa, and could face Beijing doubles gold medallists Federer and Wawrinka in the quarter finals.
In the women's doubles, top seeded American's Liezel Huber and Lisa Raymond get a pass to the second round after the withdrawal of Ukraine's Alona and Kateryna Bondarenko due to injury.
Unseeded defending gold medallists Venus and Serena Williams will take on Romania's Sorana Cirstea and Simona Halep.
Full first-round draw
R. FEDERER (SUI) v A. FALLA (COL)
A. UNGUR (ROU) v G. MULLER (LUX)
LU Y.H. (TPE) v M. JAZIRI (TUN)
L. LACKO (SVK) v I. KARLOVIC (CRO)
D. FERRER (ESP) v V. POSPISIL (CAN)
R. STEPANEK (CZE) v N. DAVYDENKO (RUS)
I. DODIG (CRO) v J.M. del POTRO (ARG)
A. BOGOMOLOV JR (RUS) v C. BERLOCQ (ARG)
G. SOEDA (JPN) v M. BAGHDATIS (CYP)
S. WAWRINKA (SUI) v A. MURRAY (GBR)
J.W. TSONGA (FRA) v T. BELLUCCI (BRA)
T. ITO (JPN) v M. RAONIC (CAN)
D. TURSUNOV (RUS) v F. LOPEZ (ESP)
D. GOFFIN (BEL) v J. MONACO (ARG)
M. CILIC (CRO) v J. MELZER (AUT)
L. HEWITT (AUS) v S. STAKHOVSKY (UKR)
A. RODDICK (USA) v M. KLIZAN (SVK)
F. FOGNINI (ITA) v N. DJOKOVIC (SRB)