You'd likely want to always use that API (or layer something on top of it) unless you're in control of both ends and know they were built with the same toolchain & settings. One area where I've skipped over it is by writing a basic code gen tool (albeit unfinished as most personal projects) that generates the serialisation functions at compile-time from a very basic DSL that describes the network structures (of a game protocol I don't control). If it detects that the current toolchain is going to generate a binary-compatible struct layout and there aren't any variable length fields in there (no strings, basically), it'll generate a memcpy (via using get/put on the stream) rather than per-field (de)serialisation. If it can guarantee alignment of the buffer, which is a tougher requirement to meet, it'll give you a view directly into the network buffer so you effectively have zero-overhead deserialisation. Very much a work in progress but there's scope for making things quite efficient with just a few basic building blocks.
I'd like to read an even more thorough overview of how it works and all the gotchas before I'd consider using this 'in production' but the API looks very easy to use and very elegant.
EDIT: just hit the section on portability, seems like you would always have to use that API, yeah? I feel like when you are writing network code you simply have to make it portable from the get-go. I guess I'm always thinking about having it run on client machines.