psspy in PSSE v33 is a 32-bit pyd and it won't work if you use a 64-bit Python interpreter to run it. 
 There is a workaround. You can call Python 32-bit interpreter in your 64-bit interpreter.
 The post is here : https://stackoverflow.com/questions/2...
 But you may need to change the "Version" to the full path of your 32-bit Python.
 Example:
 import execnet
def call_python_version(Version, Module, Function, ArgumentList):
        gw      = execnet.makegateway("popen//python=%s" % Version)
        channel = gw.remote_exec("""
            from %s import %s as the_function
            channel.send(the_function(*channel.receive()))
        """ % (Module, Function))
        channel.send(ArgumentList)
        return channel.receive()
result = call_python_version(r"C:\Python27\python.exe", "psspy", "case",  
                                 ['<path to your SAV file>'])    
print(result)
 This code should print the errorcode from psspy.case()