This study presents the synthesis of a novel composite catalyst, ZIF-67, doped on sodium bicarbonate-modified biochar derived from kumquat peels (ZIF-67@KSB3), for the enhanced activation of peracetic acid (PAA) in the degradation of acetaminophen (APAP) in aqueous solutions. The composite demonstrated a high degradation efficiency, achieving 94.3% elimination of APAP at an optimal condition of 200 mg L−1 catalyst dosage and 0.4 mM PAA concentration at pH 7. The degradation mechanism was elucidated, revealing that superoxide anion (O2•−) played a dominant role, while singlet oxygen (1O2) and alkoxyl radicals (R–O•) also contributed significantly. The degradation pathways of APAP were proposed based on LC-MS analyses and molecular electrostatic potential calculations, identifying three primary routes of transformation. Stability tests confirmed that the ZIF-67@KSB3 catalyst retained an 86% efficiency in APAP removal after five successive cycles, underscoring its durability and potential for application in pharmaceutical wastewater treatment.