To me, the most interesting thing about PNaCl is that it'll be the first real test of LLVM as a portable assembly bitcode, rather than just a compiler IR. There are arguments for why LLVM may not be such a good idea, but given the momentum it's been making, I can only see good things happening for LLVM if more people use it.
This is true for LLVM bitcode in general, but PNaCl specifies an abstract machine that defines pointers as 4 bytes long. It also specifies Little Endian &c.