I do remember a description of it in some slides a few months back, but i can't find them now.
http://www.sai.msu.su/~megera/postgres/talks/hstore-dublin-2...
How the ideas migrated from hstore to jsonb is briefly described here:
http://obartunov.livejournal.com/177247.html
http://www.postgresql.org/message-id/53304439.8000602@dunsla...
I suppose the definitive description of the format is the function JsonbToCString, which is what writes the in-memory structures out as bytes:
http://git.postgresql.org/gitweb/?p=postgresql.git;a=blob;f=...
I do remember a description of it in some slides a few months back, but i can't find them now.