2D organic materials with in-plane van der Waals forces among molecules have unique characteristics that ensure a brilliant future for multifunctional applications. Soluble organic semiconductors can be used to achieve low-cost and high-throughput manufacturing of electronic devices. However, achieving solution-processed 2D single-crystalline semiconductors with uniform morphology remains a substantial challenge. Here, the fabrication of 2D molecular single-crystal semiconductors with precise layer definition by using a floating-coffee-ring-driven assembly is presented. In particular, bilayer molecular films exhibit single-crystalline features with atomic smoothness and high film uniformity over a large area; field-effect transistors yield average and maximum carrier mobilities of 4.8 and 13.0 cm 2 V-1 s(-1), respectively. This work demonstrates the strong potential of 2D molecular crystals for low-cost, large-area, and high-performance electronics.