Platinum-catalyzed reactions of layered polysilane (Si6H6)(n) with arylacetylenes provided arylethenyl-substituted polysilanes. The polymers exhibited sigma-pi conjugation between the arylethenyl units and a catenated polysilane backbone, which was confirmed by UV-vis and PL spectral analysis. Photo-energy transfer from the arylethenyl substituents to the polysilane backbone and photocurrent generation observed in this system are also reported.