The Original Captain Marvel Vs. The Original Spider Man!
Yes, Captain Marvel battles a certain web-spinning wallcrawler in this story from Whiz Comics #89 (Sept. 1947), but this Spider Man is not Peter Parker. In fact, he looks more like an amalgam of Bela Lugosi and The Sea Hag. Still there are some similarities to Marvel's hero of some years later, like the invention that "squirts out a liquid plastic, which hardens and forms a sticky thread when it hits the air!" This story was scripted by Otto Binder and pencilled by Kurt Schaffenberger.