Organic solar cells (OSCs) are promising candidates for next-generation photovoltaic technologies, with their power conversion efficiencies (PCEs) reaching 19%. However, the typically used spin-coating method, toxic halogenated processing solvents, and the conventional bulk-heterojunction (BHJ), which causes excessive charge recombination, hamper the commercialization and further efficiency promotion of OSCs. Here, a simple but effective dual-slot-die sequential processing (DSDS) strategy is proposed to address the above issues by achieving a continuous solution supply, avoiding the solubility limit of the nonhalogen solvents, and creating a graded-BHJ morphology. As a result, an excellent PCE of 17.07% is obtained with the device processed with o-xylene in an open-air environment with no post-treatment required, while a PCE of over 14% is preserved in a wide range of active-layer thickness. The unique film-formation mechanism is further identified during the DSDS processing, which suggests the formation of the graded-BHJ morphology by the mutual diffusion between the donor and acceptor and the subsequent progressive aggregation. The graded-BHJ structure leads to improved charge transport, inhibited charge recombination, and thus an excellent PCE. Therefore, the newly developed DSDS approach can effectively contribute to the realm of high-efficiency and eco-friendly OSCs, which can also possibly be generalized to other organic photoelectric devices.