Adobe AIR program can't invoke local .exe file on Windows.
Solution
Use an AutoIt script to take over this task.
Detailed explanation
It is an interesting technique to develop an application with a Adobe AIR GUI and a Python kernel (implementing the functionalities) with PyAMF in between. (see a HelloWorld example at http://pyamf.org/wiki/HelloWorld)
On Windows machine, it is a little inconvenient that the end user has to click-open both the GUI and the kernel program to start using the application.
One solution is to use an AutoIt (a free Windows scripting environment) script: