Low molecular weight poly(2,5-dialkoxy-1,4-phenylenevinylene) polymers with branched, macrocyclic, and cyclic polyethereal alkoxy chains have been prepared by Stille cross-coupling reaction between suitable 2,5-dialkoxy-1,4-diiodobenzenes and (E)-1,2-bis(tributylstannyl)ethene. Spectral line narrowing in solution and film under high pulsed excitation intensity is reported. The measurement of the photoluminescence efficiency in film is carried out. The PPV with macrocyclic alkoxy substitution shows higher efficiency but lower damage threshold than the PPV derivative with open alkoxy chains. The potential of these materials in electroluminescent devices is discussed.