The reactivity and mechanism of the Fe-doped biochar (FeBC) Fenton reaction are typically influenced by the amount and type of Fe species in materials. This study investigated the effects of different Fe precursors (FeSO4, Fe(NO)3, FeCl2, and FeCl3) used to prepare Fenton catalyst FeBCs (FeSBC, FeNBC, FeC2BC, and FeC3BC) on the physicochemical characteristics, pH resistance, and reactivity for bisphenol A (BPA) removal. In addition to the FeSBC/H2O2 (0.007 min-1) system, FeNBC/H2O2 (1.143 min- 1), FeC2BC/H2O2 (0.278 min -1), and FeC3BC/ H2O2 (0.556 min-1) completely removed BPA within 20 min under the optimal conditions (FeBCs: 0.1 g/L; H2O2: 1 mM; BPA: 20 mg/L; pH 3). FeBCs/H2O2 systems demonstrated good stability and resistance to inorganic anions and natural organic matter under appropriate initial pH conditions. However, FeC2BC and FeC3BC exhibited better pH applicability than FeNBC. Characterization results indicated that the physicochemical properties of FeBCs were dependent on the Fe precursor, which correlated with the degree of Fe corrosion and the production of distinct reactive oxygen species (ROS). Quenching experiments and electron spin resonance detection results indicated that center dot OH, 1O2, and O2 center dot-species were all engaged in BPA removal; the ROS concentrations were significantly influenced by the initial pH and Fe precursor. The results indicate that Fe precursors significantly impact the performance and characteristics of Fe-based biochar materials, which are tailorable to specific applications.