In an effort to better understand the relationship between molecular structure and photophysical properties, we have prepared and investigated a series of novel poly(2,5-dialkoxy-p-phenyleneethynylene)s. Wide angle X-ray diffraction measurements show that the supramolecular structure can be easily and significantly influenced by the nature of substituents covalently linked to the rigid-rod polymer main chains. Polymers which have sterically hindered side chains are essentially amorphous, while those with only linear side chains can form lamellar structures with a significant degree of long-range order. High photoluminescence quantum yields, up to 0.86 in solution and 0.36 in the solid state, have been measured. While the solution quantum yields are independent of the functionalization, solid state quantum efficiencies were found to be related to the degree of long-range order in the samples. In samples with a high degree of long-range order, the close proximity of the coplanar oriented polymer backbones is assumed to lead to the formation of eximer complexes which provide non emissive decay channels and, hence, result in comparable low photoluminescence quantum yields. In samples that adopt only a small extent of long-range order, the rigid-rod conjugated polymer backbones behave as if they were ‘dissolved’ in a hydrocarbon solvent and consequently high quantum efficiencies are obtained. Preliminary results indicate the suitability of these polymers as the emitting layer in electroluminescent devices.