Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is used for the first time to characterize radio frequency plasma-deposited polymers and for investigation of the plasma polymerization process. The MALDI mass spectra of the plasma polymers of allyl alcohol, di(ethylene glycol) vinyl ether and ethylene glycol butyl vinyl ether are all reported using solvent-based MALDI sample preparation approaches. The MALDI mass spectra of each of the three plasma polymers contain distinctive polymer series ion signals having molecular weight distributions below 2000 Da. Unexpectedly, however, the ion signals from each of the three plasma polymers show a common polymer repeat unit of 44 Da, for which the chemical formula is most likely -(C2H4O)-, and no evidence of the expected radical chain polymerization polymer is detected, These results are discussed in terms of the likely involvement of gas-phase radical species having different stabilities in the radio frequency plasma environment.