Regioregular organometallic polymers with titanacyclopentadiene units, obtained from terminal diynes and a low-valent titanium complex, were subjected to reactions with disulfur dichloride and selenium (I) chloride to give p-conjugated polymers with thiophene and selenophene units in the main chain in 63% and 86% yields. Their number-average molecular weights were estimated as 4300 and 5700, respectively. Both polymers were found to be fully p-conjugated and their HOMO energy levels were remarkably high (5.3 eV and 5.0 eV for thiophene- and selenophene-containing polymers, respectively) as supported by their UV-vis absorption spectra and CV analyses.