In this study, a quaternary blending strategy was applied in the fabrication of organic photovoltaic devices and large-area modules. As a result, the ultimate quaternary organic solar cells (OSCs) deliver 16.71% efficiency for small-area devices and 13.25% for large-area (19.34cm2) modules (certified as 12.36%), which is one of the highest efficiencies for organic solar modules to date. Our results have proved the synergistic effects of multiple components in OSCs, providing an effective strategy for achieving high-performance organic photovoltaic devices and modules.