Deconvolution in Python
The function is based on Matlab's deconv, so reading that page should help understand it.

Here's a docstring I wrote for SciPy's deconvolve, but haven't submitted yet because I'm not sure it's 100% correct: https://github.com/scipy/scipy/pull/430#issuecomment-13675004

The input to deconvolve is signal and divisor, and your output is quotient and remainder, where signal was originally produced by signal = convolve(divisor, quotient) + remainder.

original = [0, 1, 0, 0, 1, 1, 0, 0]
impulse_response = [2, 1]
recorded = scipy.signal.convolve(impulse_response, original)
print recorded
# [0 2 1 0 2 3 1 0 0]
recovered, remainder = scipy.signal.deconvolve(recorded, impulse_response)
print recovered, remainder
# [ 0.  1.  0.  0.  1.  1.  0.  0.] [ 0.  0.  0.  0.  0.  0.  0.  0.  0.]


I don't understand what you're trying to do with PMFs, though, so I can't give a more specific example.