I'm not sure about "just works", but I am sure about "works" in the sense that is head and shoulders above every other video chat app I've used when it comes to audio and video quality, especially for large numbers of participants, audio sharing, document camera sharing, multiple participants sharing simultaneously, and there are plenty more.
I've never used the web version, but it wouldn't surprise me if it's not the same experience. The video and audio encoding and decoding stuff seems like it just makes more sense as a native app. Given the number of variables that browsers, versions, sandboxing, etc. bring to the equation, I can tell you where I'd spend the majority of my efforts if I were doing video chat: on a great native app. You have a lot more control over that experience, IMHO.
Anyway, your comment reads to me like someone who will never install it, but I would encourage you to at least test out the difference to see why it's become so popular.