The simultaneous detoxification processes of transformer oil-contained PCBs and heavy metals in medical waste incinerator (MWI) fly ash were developed under sub- and supercritical water. The addition of MWI fly ash to transformer oil-contained PCBs was found to increase the destruction efficiency of PCBs, at the same time, it facilitated reducing the leaching concentration of toxic metals from residues (obtained after reaction) for harmless disposal. In this study, we elucidated primarily the catalysis possibility of heavy metals in raw MWI fly ash fir PCBs degradation by adopting the sequential extraction procedure. For both MWI fly ashes, more than 90% destruction efficiency of PCBs was achieved at >= 375 degrees C for 30 min, and trichlorobenzene (TCB) existing in the transformer oil was also completely decomposed. The correlation of catalytic performance to PCBs degradation was discussed based on structural characteristics and dechlorinated products. Likewise, such process rendered residues innocuous through supercritical water treatment for reuse or disposal in landfill.