BACKGROUND The chiral pesticide bromothalonil is widely used to control anthracnose disease on fruits and vegetables in China. The pesticidal activity, ecotoxicological effects and environmental behavior of bromothalonil and its enantiomers are still unclear. RESULTS Bromothalonil presented effective biocidal activities against the tested fungi, its enantiomers showed distinct inhibitory activities against different fungal species. The bioactivities of (+)‐bromothalonil was 1.29–10.77 times higher than (−)‐bromothalonil toward Rhizoctonia solani, Botrytis cinerea, Curvularia lunata, Corynespora cassiicola, Colletotrichum siamense, and Colletotrichum musae, while the effect pattern was opposite for Colletotrichum cliviicola. Based on the acute toxicity test, bromothalonil was very toxic to Eisenia foetida (E. foetida). Bromothalonil also damaged the lysosomal membrane and exhibited potential genotoxicity toward E. foetida. Moreover, (+)‐bromothalonil presented lower toxicity than (−)‐bromothalonil. Stereoselective degradation was investigated in tomato, cucumber, chieh‐qua, and soil. The half‐life values of bromothalonil degradation ranged from 7.14 to 24.75 days, indicating that bromothalonil was easily degraded. Additionally, (+)‐bromothalonil degraded 1.2–1.75 times faster than (−)‐bromothalonil in the four matrices. CONCLUSION This is the first systemic assessment of the stereoselectivity of bromothalonil. Based on the obtained half‐life, EC50 and LC50 values, bromothalonil is an easily degraded, broad‐spectrum biocidal but very toxic pesticide. (+)‐Bromothalonil was more degradable in vegetables and soil and showed clearly higher bioactivity toward target organisms and lower toxicity to E. foetida than (−)‐bromothalonil. Therefore, the stereoselectivity of bromothalonil enantiomers should be fully considered in comprehensive environmental and ecological risk assessments in future work. © 2020 Society of Chemical Industry