Revealing the charge generation is a crucial step to understand the organic photovoltaics. Recent development in non-fullerene organic solar cells (OSCs) indicates efficient charge separation even with negligible energetic offset between the donor and acceptor materials. These new findings trigger a critical question concerning the charge separation mechanism in OSCs, traditionally believed to result from sufficient energetic offset between the polymer donor and fullerene acceptor. We propose a new mechanism, which involves the molecular electrostatic potential, to explain efficient charge separation in non-fullerene OSCs. Together with the new mechanism, we demonstrate a record efficiency of similar to 12% for systems with negligible energetic offset between donor and acceptor materials. Our analysis also rationalizes different requirement of the energetic offset between fullerene-based and non-fullerene OSCs, and paves the way for further design of OSC materials with both high photocurrent and high photovoltage at the same time.