On my Windows PC, version 0022:
C:\Documents and Settings\Owner\Desktop\arduino-0022\hardware\arduino\cores\arduino\HardwareSerial.h
C:\Documents and Settings\Owner\Desktop\arduino-0022\hardware\arduino\cores\arduino\HardwareSerial.cpp
Depends somewhat on where you installed it. So basically:
<install directory>\arduino\hardware\arduino\cores\arduino\HardwareSerial.h
<install directory>\arduino\hardware\arduino\cores\arduino\HardwareSerial.cpp