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Current research indicates that exciton dissociation into free charge carriers can be achieved in material combinations with the highest occupied molecular orbital (HOMO) offset lowered to 0 eV in non‐fullerene organic solar cells. However, the quantitative relationship between the HOMO offset and exciton dissociation has not been established because of the difficulty in achieving continuously tunable HOMO offsets. Here, the binary blends of PTQ10:ZITI‐S and PTQ10:ZITI‐N are combined to form the positive and negative HOMO offsets of 0.20 and −0.07 eV, respectively. While the PTQ10:ZITI‐S binary blend delivers a decent power conversion efficiency (PCE) of 10.69% with a short‐circuit current (J_sc) of 16.94 mA cm⁻², the PTQ10:ZITI‐N with the negative offset shows a much lower PCE of 7.06% mainly because of the low J_sc of 12.03 mA cm⁻². Because the tunable HOMO levels can be realized in organic …