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.
Federer, the top seed and world number one, will play Colombia's Alejandro Falla while Serbia's Novak Djokovic, seeded two, will face Italy's Fabio Fognini.
Women's top seed Belarusian Victoria Azarenka will play Romanian world number 79 Irina-Camelia Begu in the first round when the competition kicks off later this week.
America's Serena Williams, fresh from her fifth Wimbledon title, takes on former world number one Jelena Jankovic of Serbia.
Neither of Beijing's singles gold medallists will be returning to defend their titles, after Spain's Rafa Nadal was forced to pull out through injury and Russia's Elena Dementieva retired.
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)
J. BENNETEAU (FRA) v M. YOUZHNY (RUS)
A. UNGUR (ROU) v G. MULLER (LUX)
D. ISTOMIN (UZB) v F. VERDASCO (ESP)
J. ISNER (USA) v O. ROCHUS (BEL)
LU Y.H. (TPE) v M. JAZIRI (TUN)
L. LACKO (SVK) v I. KARLOVIC (CRO)
D. NALBANDIAN (ARG) v J. TIPSAREVIC (SRB)
D. FERRER (ESP) v V. POSPISIL (CAN)
P. KOHLSCHREIBER (GER) v B. KAVCIC (SLO)
R. STEPANEK (CZE) v N. DAVYDENKO (RUS)
B. TOMIC (AUS) v K. NISHIKORI (JPN)
G. SIMON (FRA) v M. KUKUSHKIN (KAZ)
L. KUBOT (POL) v G. DIMITROV (BUL)
A. SEPPI (ITA) v D. YOUNG (USA)
I. DODIG (CRO) v J.M. del POTRO (ARG)
T. BERDYCH (CZE) v S. DARCIS (BEL)
S. GIRALDO (COL) v R. HARRISON (USA)
A. BOGOMOLOV JR (RUS) v C. BERLOCQ (ARG)
V. TROICKI (SRB) v N. ALMAGRO (ESP)
R. GASQUET (FRA) v R. HAASE (NED)
G. SOEDA (JPN) v M. BAGHDATIS (CYP)
S. DEVVARMAN (IND) v J. NIEMINEN (FIN)
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)
- Roger Federer