Spherulitic polyparaphenylene (PPP) films were synthesized using the microemulsion-based electrooxidation of benzene. Lower polymerization charge values yielded thin films consisting of a large population of (crystalline) spherulites whereas with higher values, (amorphous) network structures were observed. A correlation was found between the thick ness-dependent morphology (and crystallinity) and luminescence characteristics. Enhancement in the crystal domain size is evident from the perfect spherulitic films.