We report the acyclic diene metathesis (ADMET) polymerization of 2,5-dipropenyl-3-hexylthiophene using ruthenium metathesis catalysts as a facile method for the production of poly(3-hexyl-2,5-thienylene vinylene) (P3HTV). Using a high-temperature polymerization under dynamic vacuum to remove the 2-butene byproduct, we were able to prepare polymers with apparent weight-average molecular weights as high as 19 kg/mol. P3HTV samples were characterized by H-1 NMR spectroscopy, size exclusion chromatography (SEC), matrix-assisted laser desorption/ionization time-of-flight(MALDI-TOF) mass spectrometry, UV-vis spectroscopy, cyclic voltammetry (CV), differential scanning calorimetry (DSC), and elemental analysis.