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Looked on [en.wikipedia.org...] but there was nothing about the origin of the word.
There are a couple of instances of "webmaster" posted to the UseNet in July 1994. Humorously, the earliest instance uses the word in the phrase "WebMaster of the Universe"
I can't remember the first time I heard the word, but I'm pretty sure it was in common use before 1994.
There are a few people here who were mastering the Web in the years pre-1994. It would take a sharp memory to recall when the term entered the SysAdmin lexicon... Perhaps in the interest of etymological geek anthropology, we could entice some of our senior colleagues to look back through their early correspondence for instances of "webmaster" ..?
Although "webmaster" implied a lot of knowledge (compared to mere non-web mortals) 12 years ago (HTML, FTP, a graphics program, maybe some CGI programming), the web has evolved a lot since then. Now a "webmaster" really does need to be a master, knowing various scripting languages, database, server administration, virus/SPAM blocking, SEO, online community building, e-commerce, PPC advertising, affiliate programs, AdSense, perhaps Flash. But realistically, too many things to be able to do all of them well ("jack of all trades, master of none").
But I feel that "webmaster" still has the same connotation from the "old" days and doesn't really reflect the skill set in use today. Anyway, that's my rant.