Rigid polymer backbones have often been considered to be detrimental to the packing of mesogenic pendants, and polyacetylenes have generally been regarded as unpromising materials for light-emitting applications. Our group, however, has succeeded in creating a series of liquid-crystalline polyacetylenes with rigid backbones and a variety of light-emitting polyacetylenes with luminescent chromophores. Here we demonstrate that the rigid polyacetylene skeleton can play a constructive role in guiding the alignments of mesogenic pendants and prove that polyacetylenes can be highly emissive with photoluminescence quantum yields of up to 98% and electroluminescence performances comparable or superior to those of the best blue-light-emitting polymers. (C) 2003 Wiley Periodicals, Inc.