Social development is accompanied by technological progress, which commonly leads to the expansion of pollution As an essential resource of modern medical treatment, antibiotics have become a hot topic in the aspect of environmental pollution. In this study, we first used fish scales to synthesize N, P-codoped biochar catalyst (FS-BC) as peroxymonosulfate (PMS) and peroxydisulfate (PDS) activator to degrade tetracycline hydrochloride (TC). At the same time, peanut shell biochar (PS-BC) and coffee ground biochar (CG-BC) were prepared as reference materials. Among them, FS-BC exhibited the best catalytic performance due to the excellent defect structure (ID/IG = 1.225) and the synergism of N, P heteroatoms. PS-BC, FS-BC and CG-BC achieved degradation efficiencies of 86.26%, 99.71% and 84.41% for TC during PMS activation and 56.79%, 93.99% and 49.12% during PDS, respectively. In both FS-BC/PMS and FS-BC/PDS systems, non-free radical pathways involved singlet oxygen (1O2), surface-bound radicals mechanism and direct electron transfer mechanism. Structural defects, graphitic N and pyridinic N, P–C groups and positively charged sp2 hybridized C adjacent to graphitic N were all critical active sites. FS-BC has the potential for practical applications and development because of its robust adaptation to pH and anions and stable re-usability. This study not only provides a reference for biochar selection, but also suggests a superior strategy for TC degradation in the environment.