This study investigates the electrochemical degradation of N,N-diethyl-m-toluamide (DEET) on PbO2 and Bi-PbO2 anodes. The difference in electrode crystalline structure was responsible for the better DEET degradation and TOC removal on PbO2 than on Bi-PbO2. In 1 M Na2SO4, the degradation efficiency and apparent rate constant (kapp) of DEET oxidation on PbO2 increased with the increase in current density or temperature (activation energy = 24.4 kJ mol−1). The kapp values in DEET-spiked environmental matrixes (municipal wastewater treatment plant secondary effluent (MWTPSE), groundwater (GW), and river water (RW)) were the same (6.05 × 10−4 s−1), but significantly smaller than that in 1 M Na2SO4 (2.23 × 10−3 s−1). The TOC removal efficiency was better in MWTPSE than in RW and GW; however, the mineralization current efficiencies in MWTPSE and RW were similar but higher than that in GW. During electrolysis, the aromaticity was lower in GW than in RW.