To monitor the role of exogenous uniconazole in mitigating chilling stress, this study investigated the effect of foliar spraying of 50 mg L−1 uniconazole on the chilling (15 °C) tolerance of mung beans at the flowering stage. The results showed that uniconazole significantly enhanced the reactive oxygen species (ROS) scavenging ability of mung beans by increasing the superoxide dismutase (SOD), peroxidase (POD), ascorbate peroxidase (APX), glutathione reductase (GR) activities, the contents of ascorbic acid (AsA) and glutathione (GSH), and the transcription levels of SOD and POD under chilling stress. The uniconazole applications also drastically increased the net photosynthetic rate (Pn), maximum net photosynthetic rate (Pnmax), maximum quantum yield of PSII (Fv/Fm), and the expression levels of the corresponding photosynthetic genes PsbO, PsbP, PsbQ, PsbY, and Psb28. This, in turn, resulted in a higher sucrose content. Meanwhile, uniconazole increased the indole-3-acetic acid (IAA) content but reduced the gibberellin A3 (GA3) content under chilling stress. During the recovery period, the photosynthetic parameters and ROS of plants receiving uniconazole recovered faster, and the antioxidant activity and non-antioxidant contents were higher than in chilling-treated plants. Additionally, chilling stress markedly reduced the pod number per plant, grain number per plant, and 100-seed weight, whereas uniconazole significantly increased the grain weight per plant by 53.47% compared to the chilling treatment. These results strongly suggest that uniconazole can effectively protect mung beans from chilling stress damage by protecting the photosynthetic machinery and enhancing the antioxidant capacity to quench excessive ROS caused by chilling stress. These effects are closely relevant to chilling tolerance enhancement and yield improvement in mung beans.