A facile synthetic route allowed access to 1,4-dimethyl-9,9-dihexylfluorene (3) with no mono-alkyl defects. Compound 3 was subsequently transformed to monomers for incorporation of 9,9-dihexyl-1,4-fluorenylene units into poly(p-phenylenevinylene) derivatives P1 and P2 via Horner-Wittig condensation and Gilch routes, respectively. The photophysical properties of P1 and P2 were characterized in solution and in solid state as thin films, and the robustness of film photophysical properties to thermal stress was evaluated. P1 and P2 appear to be the first pi-conjugated polymers incorporating 9,9-dialkyl-1,4-fluorenylene units.