The difference between Win32 and MFC are pretty straightforward:
The Windows API (Win32) uses a C interface to access windows functionality. It requires that you write all of your own code to manage windows and message handling. It is quite straightforward but you will need a good reference, like MSDN, and some good tutorials or samples to get started.
In contrast, MFC, which stands for Microsoft Foundation Classes, are a collection of C++ classes which encapsulate the Win32 API. MFC has some wizards which make the initial creation of a program quick and easy, but I have to admit the learning curve of MFC can sometimes be frustrating as Microsoft seems to have done everything in a way that can at times seem counter-intuitive.
Whenever I write an application I write it in MFC but I have been writing applications in MFC for a long time. If all you want is a message loop and a window handle for a game, use Win32. If you want to write a larger application like an editor, maybe MFC is the right tool.
Ideally, I would suggest skipping both Win32 and MFC and writing tools in .NET. I do not have any personal experience in it but people I work with sure can get a lot done using it. It may well be worth investigation.
Best of luck,
- S
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