It provides API layer which compiles to Win32 API on Windows, Gtk2 on Linux and Carbon/Cocoa on Mac OSX.
Qt only emulates Windows controls, but wxWidgets uses the actual Windows controls via Microsoft Win32 API.
BTW, there's wxQt, a wxWidgets implementation that uses Qt instead of Gtk, but it's still experimental:
https://wiki.wxwidgets.org/WxQt
wxWidgets has been used by some popular projects like Audacity, TortoiseCVS, RapidSVN, FileZilla, BitTorrent, etc.
Another wxWidgets advantage over Qt is the license, which gives you more freedom.
If you're looking for a faster start, take a look at wxFormBuilder which is a graphical WYSIWYG UI editor where you can drop controls in windows/dialogs and hook up event handlers.
You can find links to more related tools/IDEs on the Wikipedia page: