The low nitrogen use efficiency (NUE) of fertilizers and aluminum toxicity are major limiting factors for crop development in red soil (acidic soil) of China. Biochar is a promising material for improving soil quality, alleviating aluminum and acidic toxicity. The present study was conducted on maize to evaluate the effects of biochar on NUE and soil quality under different applications of nitrogen fertilizer. Biochar was used in the following five levels in each pot; C0 (0 g), C1 (7.5 g), C2 (15 g), C3 (30 g), C4 (45 g), in combination with δ¹⁵N at two N levels: N0 (0 g kg⁻¹) and N1 (0.2 g kg⁻¹). The biochar increased soil nutrients, exchangeable cation, and SOM. Compared with C0, the K⁺, Ca²⁺, and Mg²⁺ were increased by 31.58%, 95.87%, and 463.75% while total Al³⁺ content of C4 treatment was decreased by 91.98%–93.30% in soil, respectively. X-ray diffraction (XRD) and energy dispersive spectrometer (EDS) showed that Al₂SiO₅ was adsorbed on the surface of biochar in the soil due to the special physical structure of biochar. Besides, the results showed that root and shoot biomass increased by 44.5% and 89.6%, respectively under biochar treatment. The nitrogen utilization rate of the plant was increased by 11.08% after the amendment of biochar to soil. The δ¹⁵N content was increased from 11.97 to 21.32 for root and from 50.84 to 82.33 mg kg⁻¹ for the shoot. The use of biochar with N fertilizer showed a more positive effect on improving NUE of maize and facilitating soil quality. Our results suggest that biochar could be used to improve soil available nutrients, alleviate aluminum toxicity and acidic toxicity. Therefore, biochar could also increase the NUE of maize by adjusting soil quality.