Photoluminescence (PL), electroluminescence (EL) and degradation of a soluble electroluminescent poly(p-phenylene), poly[2,5-bis(isopentyloxy)-1,4-phenylene] (SPPP), and its blends with hole transport polymers based on poly[methyl(phenyl)silandiyl] (PMPSi) were studied. Efficient blue light-emitting devices (LEDs) with an air-stable (Al) electrode based on polymer blends composed of SPPP and PMPSi have been fabricated. In contrast to LEDs made of neat SPPP, an increase in external EL efficiency (up to 30 times) and improvement of the stability of blue emission were achieved in these LEDs. This enhancement is far above the increase in the PL efficiency of the blend layers. New alternately substituted poly(p-phenylene)s with high photoluminescent efficiency and new polymers with pi-conjugated (pyrene, biphenyl) or electron-transporting (oxadiazole) moieties attached to the polysilane backbone were synthesized.