The effect of double blocking layers on the Sb(2)S(3)-sensitized all solid state solar cell are investigated. Thin layers of ZrO(2) (blocking layer 1, BL1) and ZnS (blocking layer 2, BL2) are introduced at the TiO(2)/Sb(2)S(3) and Sb(2)S(3)/hole transporting material (HTM) interfaces. The presence of BL1 is found to improve the open-circuit voltage (V(oc)) from 457 mV to 618 mV, whereas BL2 improves mainly short-circuit current density (J(sc)) from 11.1 mA cm(-2) to 14.0 mA cm(-2). Transient photovoltage confirms that the BL1 efficiently blocks charge recombination, responsible for the V(oc) enhancement, whereas the BL2 has little effect on suppression of charge recombination. Surface modification of Sb(2)S(3) by BL2, on the other hand, leads to recovery of Sb(2)S(3) from the surface oxidized Sb(2)O(5), which affects the J(sc) increment. The present results suggest that the TiO(2)/Sb(2)S(3) interface is the main pathway for charge recombination rather than the Sb(2)S(3)/HTM interface. Double blocking layers enhanced the power conversion efficiency by 30%.