TOF-SIMS measurements of a thick film 1 kDa polystyrene functionalized with a perfluoroalkyl endgroup are presented. Characteristic fragment signals in the low mass range are observed. The thick film of 1 kDa functionalized polystyrene is also analyzed with an overlayer of silver. This modification in sample preparation allows intact oligomer signals to be generated from the surfaces of thick films (i.e., in bulk form) of low molecular weight polymers.