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Rapeseed meal, a nutritious organic fertilizer (OF), contributes to improving soil environment and crop productivity. However, there are also problems, namely slow fertilizer efficiency and low nutrient utilization during the growing season. This 2‐year field trial was conducted to explore the effect of biochar addition on improving the nutrient availability of OF through a comparative study of various biochar application rates under rice‐rapeseed rotation conditions. The findings revealed that, compared to the individual application of chemical fertilizers (CF), OF alone decreased rice yield (2%/2%) and rapeseed yield (6%/10%) in 2019/2020. Compared with OF, combining biochar (15 t ha−1) with OF (OF + B15) significantly increased rice yield (17%/10%) and rapeseed yield (25%/20%) in the first/second year. Additionally, OF + B15 still increased rice yield (14%/7%) and rapeseed yield (12%/13%) for two consecutive years compared to CF. The co‐application of biochar and OF had positive impacts on soil physicochemical properties and enzymes. Compared to OF, OF + B15 elevated soil organic carbon (SOC) by 57%–81%, soil catalase 19%, invertase 14%–20%, urease 17%–19%, and phosphatase 13%–17% during rice season, and similarly increased SOC by 77%–90%, soil catalase 14%–16%, invertase 14%–20%, urease 18%–24%, and phosphatase 16%–17% in rapeseed season. Biochar addition improved soil conditions and enzymatic activities, and the available nutrient supply of OF. Also, the co‐application of biochar and rapeseed meal surpassed the effect of chemical fertilizer alone on the growth and yield of crops. Therefore, biochar coupling with organic fertilizer is an effective fertilization strategy based on resource recycling, which promotes both crop yield and sustainable agriculture. [ABSTRACT FROM AUTHOR]