Liquid-crystalline 3,3′-dimethyl-2,2′-bipyridyl derivatives with long 4-(alkoxyphenyl)ethynyl groups at the 5,5′-positions were synthesized by palladium-catalyzed cross-coupling reaction, and the obtained compounds exhibited only the nematic phase as the liquid-crystalline phase. And liquid-crystalline 3,3′dimethyl-2,2′-bipyridyl derivatives with long 4-(alkoxyphenyl)ethynyl groups showed quantum yields higher than 45% in photoluminescence.