You need to cast to a pointer type, i.e. POINTER(Struct). Trying to cast to just Struct should raise a TypeError. Instead this revealed a bug in cast_check_pointertype (3.4.1):

http://hg.python.org/cpython/file/c0e311e010fc/Modules/_ctypes/_ctypes.c#l5225

dict->proto is NULL in the Struct type's stgdict, so PyUnicode_Check(dict->proto) segfaults. A simple fix is to add a check for this on line 5235:

    if (dict && dict->proto) {

Then cast will raise the expected TypeError from line 5242 on return from line 5255.