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Organic photovoltaics (OPVs) with three types of double anode buffer layers (DABLs), i.e., 4.5 nm hole-transport material 4,4-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl layer, 1 nm electron-transport material Bphen, and 1 nm typical insulator LiF layer, respectively, deposited onto 10 nm MoO3 layer, were fabricated. All these three DABLs can improve the efficiency of CuPc/C60 based planar heterojunction OPV, especially with about 10% enhancement of short-circuit current (ISC). Based on the external quantum efficiency (EQE) and transient photovoltage (TPV) measurements, a mechanism of depressing harmful exciton dissociation at the MoO3/CuPc interface has been proposed. This harmful dissociation results in exciton loss within the CuPc layer, while a proper ultrathin layer inserted at MoO3/CuPc interface can effectively depress the dissociation and thus improve the total photocurrent.