As usual, it depends on what you consider 'the first real ...'. If you limit it to serial protocols, then you might end up quite late ('90s or '00s). Parallel protocols were much earlier. Something like a word recognizer might not qualify since its decoding is extremely limited, but something like a Tektronix DF2 (could decode GPIB) or DF1 (format a parallel bus as a list of hex/binary states) could arguably qualify, through you could argue if this was for a logic analyzer (7D01) that happened to use a scope as display, rather than a scope. This stuff would have been mid-70s.
A HP 59401A Bus System Analyzer (would display the current status of an HPIB/GPIB bus with lights and allowed you to send messages using toggle switches), also around mid-70s, could be argued to be a stand-alone protocol decoder (similar to the TotalPhase products available these days). The HP 1601 logic analyzer (mid-70s) could do basic state display, and the later 1611 (late 70s or early 80s) could do actual inverse assembly, which I would consider a fairly sophisticated kind of protocol decoding.
So based on a quick look in a few Tek/HP Catalogs, I would place the first products around mid-70s. Basically when digital design and computer design started to take off.