An autocatalytic system, permanganate-ultrasonic (PM-US) system, was applied to degrade perfluorooctanoic acid (PFOA) in aqueous solutions. After a 120-min ultrasonication, a PM dosage of 6 mM increased the pseudo first-order rate constant (k1) for PFOA decomposition from 3.5 × 10-3 to 13.0 × 10-3 min-1 and increased the pseudo zeroth-order rate constant (k2) for PFOA defluorination from 1.5 × 10-3 to 7.9 × 10-3 mM·min-1, respectively. The PFOA degradation rates increased proportionally with the enhanced production rates of MnO2 particles. An initial pH 4 condition was optimal for the PFOA degradation compared to highly acidic and neutral conditions. PFOA degradation could be significantly facilitated by increasing power density of ultrasonication from 60 to 180 W·L-1. While increasing solution temperature to 50 °C only slightly promoted the PFOA decomposition and defluorination to 1.15 and 1.07 times of that at 30 °C, respectively. The solution saturated with argon was more favorable for the PFOA degradation in the PM-US system than that saturated with air and oxygen. Co-dissolved Cu(II), Fe(II) and Fe(III) ions inhibited the PFOA degradation by forming metal-PFOA complexes. Based on the experimental results and intermediates analysis, mechanisms and pathways of PFOA decomposition and defluorination in the PM-US system were proposed.