Who says it's about Win32?
The Win32 API is huge and closed. The Wine team have tried to re-implement it from scratch and had remarkable results. But it wasn't enough.
To run Windows applications you need the Win32 API and the complete surroundings, the interface, the expected behaviour of the rest of the OS, and the GUI that fits the applications. Win32 programs are not designed to run on anything but Windows and emulating Windows doesn't solve that problem.
If you want to run Windows programs, run Windows; that's what it's for. Choose between the Ferari and the Maserati, don't ask the mechanic to combine the two.
I am sure that is not what the PE support is for.
But the Portable Executable format is not only used for Win32 programs.
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PE was used by BeOS 3.x for Intel BeOS programs. It is also used by Interix for UNIX-based programs running on Windows.
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It is also used as the native format for .NET applications.
Now, in contrast to Win32 the .NET API is standardized, well-documented, and several implementations exist. In fact Novell's implementation works really well on Mac OS except for the fact that X11 is needed (for all .NET programs that don't use Cocoa or the console) and the fact that .exe files cannot be easily started on Mac OS X.
.NET programs are also meant to be cross-platform and not supposed to depend on Windows peculiarities.
Portable Executable .exe files do not run on Linux either, unless one compiles a kernel that has support for .exe files.
Mac OS X appears to be implementing a feature of Linux: support for the PE executable format. That's it.
So perhaps Apple (and maybe Novell) are working on a Cocoa-native implementation of Mono (Novell's .NET implementation). I know Novell were working on a Carbon implementation.