TOF-SIMS measurements of 5 and 40 kDa polystyrene functionalized with a perfluoroalkyl endgroup are presented. Fragment signals in the low mass range are observed for both 5 and 40 kDa samples, using monolayer sample preparation on a silver substrate. Additionally for the 5 kDa sample, intact oligomer signals in the high mass range and chain cleavage signals in the intermediate mass range are generated. The successful functionalization of the polystyrene with the perfluoroalkyl endgroup can be confirmed by the masses at which the intact oligomer signals arise.