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Intense photoluminescence (PL) was observed in soluble disubstituted polyacetylenes such as poly(1-phenyl-2- p-adamantylphenyl acetylene (PDPA-Ad) at 530 nm, poly(1-phenyl-2- p-triphenylsilylphenyl acetylene) (PDPA-TPSi) at 530 nm and poly(1-hexyl-2-phenyl acetylene) (PHxPA) at 455 nm, although they are considered to be derivatives of trans-polyacetylene. In monosubstituted acetylene polymers such as poly( o-trimethylsilylphenyl acetylene) (PTMSiPA), PL was negligible. Green and blue light emissions were observed from an electroluminescent (EL) device having soluble poly(diphenyl acetylene) (PDPA) derivatives (PDPA-Ad and PDPA-TPSi) and PHxPA as emission layers, respectively. EL emission is clearly observable under normal room illumination conditions. The electronic energy structures of the disubstituted PA derivatives are also discussed to interpret PL and EL characteristics.