This work details the synthesis of a functionalized all-donor polymer, poly(3-hexylthioacetate thiophene) (P3HTT). The spectrophotometry analysis of the polymer showed absorption bands at 450 and 536 nm in the liquid and solid states, respectively with optical band gap ( QUOTE ) of 1.9 eV. In addition, the polymer emits in the green region of the emission spectrum with photoluminescence (PL) QUOTE of 579 nm and 26% photoluminescence quantum yield (PL Φ). The highest occupiedmolecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the polymer were found to be -5.05 and -2.9 eV, respectively. Dye-sensitized solar cells(DSSCs) devices based on this polymer were fabricated in combination with nano-crystalline titanium dioxide (nc-TiO2) and ruthenium 535-bis tetrabutylammonium (TBA) dye to give devices with the configuration, glass/SnO2:F/nc-TiO2/dye/polymer/Au. The best device showed power conversion efficiency (PCE) of 0.035% with Voc, Jsc and FF of 610 mV, 1.7 mA/cm2 and 34%, respectively.