Atmospheric pressure Solids Analysis Probe (ASAP) mass spectrometry has facilitated the ionisation of oligomers from low molecular weight synthetic polymers, poly(ethylene glycol) (PEG: M n = 1430) and poly(styrene) (PS: M n = 1770), directly from solids, providing a fast and efficient method of identification. Ion source conditions were evaluated and it was found that the key instrument parameter was the ion source desolvation temperature which, when set to 600 °C was sufficient to vapourise the heavier oligomers for ionisation. PS, a non-polar polymer that is very challenging to analyse by MALDI or ESI without the aid of metal salts to promote cationisation, was ionised promptly by ASAP resulting in the production of radical cations. A small degree of in-source dissociation could be eliminated by control of the instrument ion source voltages. The fragmentation observed through in-source dissociation could be duplicated in a controlled manner through Collision-Induced Dissociation (CID) of the radical cations. PEG, which preferentially ionises through adduction with alkali metal cations in MALDI and ESI, was observed as a protonated molecular ion by ASAP. In-source dissociation could not be eliminated entirely and the fragmentation observed resulted from cleavage of the C-C and C-O backbone bonds, as opposed to only C-O bond cleavage observed from tandem mass spectrometry.