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Abstract A 28 days pesticide degradation experiment was conducted for broccoli (Brassica oleracea L. var. italica Planch) and pakchoi (Brassica chinensis L.) with three pesticides (chlorantraniliprole (CAP), haloxyfop-etotyl (HPM), and indoxacarb (IXB)) to explore the effects of biochar on pesticide environmental fate and rhizosphere soil diversity. Rice straw biochar (RB) was applied to soil at a 25.00 t ha−1 dosage under greenhouse conditions, and its effects on the degradation of three pesticides in vegetables and in soil were investigated individually. Overall, RB application effectively facilitated CAP and HPM degradation in broccoli by 13.51–39.42% and in broccoli soil by 23.80–74.10%, respectively. RB application slowed the degradation of CAP, HPM and IXB in pakchoi by 0.00–57.17% and slowed the degradation of CAP in pakchoi by 37.32–43.40%. The results showed that the effect of RB application on pesticide degradation in crops and soil was related to biochar properties, pesticide solubility, plant growth status, and soil characteristics. Rhizosphere soil microorganisms were also investigated, and the results showed that biochar application may be valuable for altering bacterial richness and diversity. The effect of biochar application on pesticide residues in crops and soil was influenced by the vegetable variety first, and the second was pesticide characteristics. RB applied to soil at a 25.00 t ha−1 dosage under greenhouse conditions is recommended for broccoli production to ensure food safety. Our results suggested that biochar application in soil could reduce pesticide non-point source pollution, especially for highly soluble pesticides, and could affect soil microorganisms.