Amphiphilic hybrid pi-conjugated polymers that have polyhedral oligomeric silsesquioxanes on their side chains have been successfully synthesized by the Sonogashira-Hagihara poly-condensation reaction. The obtained polymers were studied with ultraviolet-visible absorption and photoluminescence spectra. In these polymers, the pi-conjugation length was extended along the poly(p-phenylene-ethynylene) backbone. Furthermore, the content of the POSS substituents can influence the aggregation behavior of the polymers and subsequent luminescent properties.