New soluble polysilane copolymers which were made up of diphenyl and dimethylsilylene segments, were prepared successfully by condensation reaction of 1,5-dilithiodecaphenylpentasilane and the corresponding α, ω-dichloropermethyl oligo- silanes. The polysilane copolymers showed emission in a near-ultraviolet region. As an application of organic thin-film devices, we fabricated 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4,-oxadiazole(PBD)/ poly(9,9-di-n-octylfluorenyl-2,7-diyl)(PFO) layers by wet process and attained higher emission efficiency under lower operating voltage.