Your first step would be to look for the 4-byte sequence
PE\0\0
which is the signature of a PE header.
Following that, look for any valid architecture code (or if you expect say just the Intel architecture, look for that specific architecture code)
0x14d Intel i860
0x14c Intel I386 (same ID used for 486 and 586)
0x162 MIPS R3000
0x166 MIPS R4000 0x183 DEC Alpha AXP
Depending on other data on the wire, and on your needs, that may be enough to reasonably assume the the data represents a PE binary and you may wish to attempt to load the data as an executable at that point. If you must have absolute confidence, you will need to parse the header just like a the loader would. Complete information on the PE structure can be found at