Fluorescence (FL) emission properties, microporous structures, energy-minimized chain conformations, and lamellar layer structures of the silicon-containing poly(diphenylacetylene) derivative of p-PTMSDPA before and after desilylation were investigated. The nitrogen-adsorption isotherms of p-PTMSDPA film before and after desilylation were typical of type I, indicating microporous structures. The BET surface area and pore volume of the p-PTMSDPA film were significantly reduced after the desilylation reaction, simultaneously, its FL emission intensity remarkably decreased. The theoretical calculation on both model compounds of p-PTMSDPA and its desilylated polymer, PDPA, showed a remarkable difference in chain conformation: The side phenyl rings of p-PTMSDPA are discontinuously arranged in a zig-zag pattern, while the PDPA is continuously coiled in a helical manner. The lamellar layer distance (LLD) in the p-PTMSDPA film significantly decreased after the desilylation reaction.