Poly(silylene-p-phenylene)s bearing an anthrylethynyl, pyrenylethynyl, or terthienyl group as the pendant were obtained in moderate yield, by substitution reactions of poly [ethoxy(methyl)silylene-p-phenylene] with the corresponding organolithium reagents in THF. The polymers exhibited photoluminescent (PL) properties in solutions as well as in the films. They were photoactive and irradiation of the films in air with a low-pressure mercury lamp led to a decrease of PL efficiencies, being applicable to PL imaging of the films. The present polymers can be used also as hole-transporting materials in double-layer electroluminescent (EL) devices and the devices with the structure of ITO/polymer film/Alq3/Mg-Ag emitted a green EL arising from Alq3 emission.