The Dwarf-2 EH implementation for Windows is not designed at all to work under 64-bit Windows applications. In win32 mode, the exception unwind handler cannot propagate through non-dw2 aware code, this means that any exception going through any non-dw2 aware "foreign frames" code will fail, including Windows system DLLs and DLLs built with Visual Studio. Dwarf-2 unwinding code in gcc inspects the x86 unwinding assembly and is unable to proceed without other dwarf-2 unwind information.
The SetJump? LongJump? method of exception handling works for most cases on both win32 and win64, except for general protection faults. Structured exception handling support in gcc is being developed to overcome the weaknesses of dw2 and sjlj. On win64, the unwind-information are placed in xdata-section and there is the .pdata (function descriptor table) instead of the stack. For win32, the chain of handlers are on stack and need to be saved/restored by real executed code.