The effects of organic dye, pyran-4-ylidene-2-cyanoacetate derivative, and annealing on the dye-doped bulk heterojunction photovoltaics (PV) based with poly(3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-(6,6)C61 (PCBM) have been investigated. The structures of the PV cells were ITO/PSS:PEDOT/P3HT:PCBM (1:1 wt.%)/Al and ITO/PSS:PEDOT/P3HT:PCBM:Pyran-4-ylidene-2-cyanoacetate derivative (1:1:0.5wt.%)/Al electrode. Using the thermal treatment of the PV cell containing the organic dye at 140C for 5min, an increase in power conversion efficiency to 2.0% and external quantum efficiency (IPCE) to 36% are demonstrated.