The first anthracene-containing conjugated polymer, poly(1,4-anthrylenevinylene) (PAV), was synthesized. Its processability was accomplished by using the precursor polymer route. Consideration of the mechanism responsible for the polymerization reaction led to selection of the adequate monomer to achieve polymerizability. UV spectra of PAV films showed a band-gap energy 0.3 eV smaller compared to that of poly(phenylenevinylene) (PPV) as a result of the minimization of the energy difference between aromatic and quinoid resonance structures by the anthracene unit. Model compound 13 was synthesized to exclude structural defects of PAV as well as to clarify the role of the steric and electronic effects on the conformation of the main chain. The optical properties of PAV thin films drastically changed upon reaction with a dienophile in the solid state.