"I like watching movies online."
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I don't think they've made it clear anywhere, but 上 sometimes acts like a verb or a verb phrase, meaning "to get onto" or "to mount". 网 is literally "net", so 上网 is really something like "to get onto the (internet)", i.e. "to go online", as opposed to simply an adverb or adjective ("online"). So you can say "I like to go online (and / in order to) watch movies", but not "I like to watch movies to go on line".
I think that 上网 acts as an adverbial because it describes how the films are watched, and an adverbial usually goes before the verb it qualifies. Mandarin is more strict about the positioning of adverbials than English which basically puts them all over the place including at the end of the sentence as in this case.
You are right about adverbials in general, but 上 is a verb here (to get on/to turn on) and 网 (net, internet) is its object. Chinese almost always puts verbs in sequential order. The speaker goes online in order to watch movies. Going online has to happen before watching the movie can start. So, 上网 comes before 看电影.