Transition metal-catalyzed addition of bis-silyl hydride to bis-alkyne is widely used for the synthesis of alt-silylene-divinyl-linker copolymer. When the linker for connecting two silyl hydrides is different from that for two alkyne motifs, hydrosilylation reaction will give the corresponding AB-type copolymer. The reactivity of alkynes can be manipulated by using different protective groups. This kind of strategy would enable us to assemble a range of linkers in regioregular manner or sequence-controlled tactic. In this account, we summarize our synthetic endeavors on the use of rhodium-catalyzed hydrosilylation reaction to incorporate different kinds and/or numbers of chromophores arranged regioselectively on the polymeric backbone. The photophysical properties such as those arising from the ground state interactions, fluorescence resonance energy transfer, photoinduced electron transfer, light-harvesting, or a combination thereof have been systematically examined. These data may offer useful clues on the folding behavior of these silicon-containing polymers.