The internet is the scaffolding/structure, the Web is what people are doing in a browser (i.e., over HTTP) in it.
Then there's also the stuff people do on the internet without a browser/HTTP. Nobody opens an IMAP/SSH/BitTorrent/IRC client or whatever and thinks of that as surfing the Web, because those aren't browsers nor are they primarily speaking HTTP.
The structure allows for great things. People suck. Hell is other people and all that.