We demonstrate the working mechanism of organic photovoltaic (OPV) cell with copper phthalocyanine (CuPc) as exciton blocking layer (EBL). The new EBL material CuPc, commonly has been used as electron donor in the organic solar cells due to its electron-donating and hole-transporting properties. But here we proves that the α-polymorph CuPc layer can transfer electrons to Al cathode through the half-filled b 1g level, this mechanism is different from that of general EBL material with larger band gap and electron-transporting property, which is based on damage states induced by the heat of evaporating Al.