Enabling green-solvent-processed large-area organic solar cells (OSCs) is of great significance to their industrialization. However, precisely controlling the temperature-dependent fluid mechanics and evaporation behavior of green solvents with high-boiling points is challenging. Controlling these parameters is essential to prevent the non-uniform distribution of active layer components and severe molecule aggregation, which collectively degrade the power conversion efficiency (PCE) of large-scale devices. In this study, we revealed that the temperature gradient distribution across a wet film is the root of the notorious Marangoni effect, which leads to the formation of a severely non-uniform active layer on a large scale. Thus, a rapid solidification strategy was proposed to accelerate the evaporation of toluene, a green solvent, at room temperature. This strategy simultaneously inhibits the Marangoni effect and suppresses molecular aggregation in the wet film, allowing the formation of a nano-scale phase separation active layer with uniform morphology. The resultant toluene-processed 15.64-cm2 large-area OSC module achieves an outstanding PCE of 16.03% (certified: 15.69%), which represents the highest reported PCE of green-solvent-processed OSC modules. Notably, this strategy also exhibits a weak scale dependence on the PCE, and we successfully achieved a state-of-the-art PCE of 14.45% for a 72.00-cm2 OSC module. A rapid solidification strategy was developed for simultaneously avoiding the Marangoni effect and suppressing molecular aggregation. The resultant 15.64 cm2 large-area OSC module exhibited a record power conversion efficiency of 16.03%.