AbstractInspired by the 2D bilayer lipid membranes in nature, a unique supramolecular “push–pull” synergetic strategy toward self‐assembled 2D organic crystals (2DOCs) is proposed in this work, which can effectively suppress the interlayer 3D stacking while maintaining the assembly of the intralayer for 2D growth. For this purpose, a model molecule PF‐Py consisting of a planar supramolecular “attractor” and a nonplanar steric “repellor” is designed for the solution self‐assembly process. Well‐defined 2DOCs including crystal nanosheets and millimeter‐sized crystal films with layered amphiphile‐like packing are obtained, which is analogical to the cell membranes of living organisms. Thanks to the special packing mode, the 2DOCs have fascinating integrated photoelectric property, with high mobility of 7.8 × 10⁻² cm² V⁻¹ s⁻¹, high crystalline state photoluminescence quantum yield of 55%, and superior deep‐blue laser characteristics with a low threshold of 5.51 µJ cm⁻². This supramolecular synergetic strategy advances the design of 2D organic semiconductor crystals for high performance optoelectronics.