A series of novel hybrid organic-inorganic light-emitting materials, polyhedral oligomeric silsesquioxane-tethered poly(fluorenyleneethynylene)s, were successfully synthesized via Sonagashira coupling reaction. The chemical structures of these copolymers were determined by H-1 NMR and FT-IR spectra. The morphologies of these copolymers were studied in details using TEM and WAXD. The WAXD data showed that POSS formed aggregation instead of crystallization in the polymer matrix, indicating the significant effect of the backbone constraint on POSS crystallization. Furthermore, it also revealed that the interchain interaction weakened and the interchain distance increased after introducing POSS groups. The TEM data indicated that POSS aggregates were well dispersed in polymer matrix. In accordance with the morphological investigation, the results of UV-vis absorption and photoluminescence emission spectra of these copolymers showed that the tendency toward planar conformation of conjugated backbones reduced to a certain extent due to weakened interchain interaction. Accordingly, these copolymers exhibited the enhanced quantum yields in the solid state. In addition, owing to the thermal and oxygen stability of hybrid POSS, the thermal spectral stability of these polymers was also improved greatly. (c) 2006 Elsevier Ltd. All rights reserved.