A new method is described for the synthesis of soluble poly(1-methoxy-4-(2-ethylhexyloxy)p-phenylenevinylene) (MEH-PPV) using N,N-dimethylformamide (DMF) as the solvent. Based on a modification of the traditional Gilch method, the polymerization of alpha,alpha'-dibromo-2-methoxy-5-(2-ethylhexyloxy)xylene was conducted in DMF under a variety of experimental conditions. The resultant MEH-PPVs were characterized and compared to those prepared using analogous syntheses in tetrahydrofuran (THF). Characterization techniques included H-1 NMR spectroscopy, UV-vis spectroscopy, and gel permeation chromatography (GPC). Although the molecular weights of the polymers prepared in DMF were routinely lower than those prepared in THF, the polydispersities were as low as (and in most cases lower than) those obtained using THF. Significantly, the use of DMF in polymerizations conducted at 100 degreesC led to no gelation of the polymer, which circumvented the need for any controlled addition of monomer during the reaction. Moreover, control over the polymer molecular weights in DMF could be achieved using chosen aliquots of the molecular weight modifier 4-(tert-butyl)benzyl bromide and/or by controlling the concentration of the reactants.