In this study, we first comprehensively studied peroxymonosulfate (PMS) and peroxydisulfate (PDS) activation mechanisms using N, O codoped sludge biochar (NOSB) to degrade organics from water. Among the catalysts, NOSB with a higher content of graphitic N, optimal edge nitrogen (pyridinic N and pyrrolic N), CO groups, sp2-hybridized C, and rich defects were demonstrated to be a superior catalyst. Therefore, by activating PDS and PMS, NOSB exhibited the highest rate of BPA degradation, which was 22-fold and 13-fold that of pristine sludge biochar, respectively. However, owing to different oxidation potentials and molecular structures, PMS and PDS show different degradation performances due to various catalytic mechanisms occurring, even with the same biochar. Due to the asymmetrical structure of PMS, electrons passed from PMS to NOSB and further generated singlet oxygen (1O2), which governs the degradation of bisphenol A with an auxiliary contribution of single electron transfer. Meanwhile, PDS is reduced at the Lewis basic sites of NOSB, forming inner-surface-bound {PDS-NOSB}, which was oxidizing around neighboring carbon and decomposed targets through transferring single and double electrons. NOSB is promising for practical applications because of its adaptation to a wide pH range, anions, high total organic carbon removal, tunable active sites, and re-usability for degrading organics via PMS/PDS activation. This study unveils knowledge about N, O codoped sludge biochar catalysts for activating PMS/PDS and advocates a great approach for organics’ degradation in the environment.