AbstractRecombining the advantages on photovoltaic parameters of two binary‐organic photovoltaics (OPVs) into one ternary cell is an efficient strategy for selecting materials, in addition to the absorption spectra complementary among the used materials. The binary‐OPVs with J71:BTP‐4F‐12 exhibit a power conversion efficiency (PCE) of 11.70%, along with a short‐circuit‐current‐density (JSC) of 23.61 mA cm−2, an open‐circuit‐voltage (VOC) of 0.841 V and a fill factor (FF) of 58.99%. Although the relatively low PCE of 10.92% and JSC of 16.59 mA cm−2 are achieved in J71:ITIC‐based binary‐OPVs, the VOC of 0.935 V and FF of 70.40% are impressive compared with J71:BTP‐4F‐12‐based OPVs. Optimal ternary‐OPVs are achieved with J71:BTP‐4F‐12:ITIC as active layers by weight ratio of 1:0.48:0.72, delivering a markedly increased PCE of 13.05% with a VOC of 0.903 V, a JSC of 21.27 mA cm−2 and a FF of 68.20%. An over 11.5% PCE improvement is obtained by recombining the advantages of binary‐OPVs into ternary‐OPVs with ITIC as photon harvesting reinforcing agent and morphology regulator. The good compatibility between BTP‐4F‐12 and ITIC provides large room to well optimize their relative content for achieving the well balanced three key photovoltaic parameters of ternary‐OPVs.