Sol-gel processing represents a promising method of fabrication for thin films of electronic ceramics which are useful in packaging and device applications. In this study, the influence of acid and base catalysts on the structure of PbTiO//3 gels and films (0. 1-1. 0 mu m) was investigated for the purpose of identifying gel structures which are suitable as precursors for thin dielectric layers. Continuous crack-free solutions gelled rapidly, phase separated, and were probably more crosslinked than acidic gels. Acidic gels seemed more capable of polymeric rearrangement during drying, yielding denser amorphous structures with microcrystalline regions. High-field dielectric constants (1 MV/m ac) in the range K equals 30-40 and K equals 160-170 were determined for amorphous and crystalline films, respectively.