Environmentally friendly antisolvents are key to achieving efficient, reproducible, and sustainable perovskite solar cells (PSCs). Here, a comparison was made between the traditional highly toxic chlorobenzene (CB) antisolvent and green antisolvents ethyl acetate (EA) and dimethyl carbonate (DMC). The employment of green antisolvent DMC was shown to result in the formation of perovskite films with enhanced grain size and superior crystal quality. This leads to an optimal energy level alignment with the electron transport layer, effectively mitigating the nonradiative recombination caused by film imperfections, reducing the loss of organic components during the annealing process, and suppressing the formation of the lead iodide phase. Finally, the champion device, based on the antisolvent DMC, exhibited a high power conversion efficiency (PCE) of 25.18%, which is one of the high PCEs reported for this device structure. Moreover, the device maintains 92% of its original PCE after approximately 1000 h under environmental conditions.