A new synthetic route was developed to obtain highly regioregular poly[(2-methoxy-5-alkyloxy)-1,4-phenylenevinylene]s (PPVs) by the Horner reaction using asymmetrically functionalized monomers. The polymers showed good solubility in chlorobenzene at over 100 degrees C. The high regioregularity of the polymers was confirmed by H-1 NMR quantitative analysis using chlorobenzene-d(5) as solvent, which was developed for the first time in this study. Assignment of the H-1 NMR peaks was conducted by synthesizing four novel model compounds for PPV. UV-vis, fluorescence spectra, and XRD data revealed that these regioregular PPVs have higher crystallinity compared to regiorandom PPVs in the solid state.