The crystal structure has a significant impact on the electrochemical properties of electrode material, and thus influences the electrocatalytic activity of the electrode. In this work, alpha-, beta-, and gamma-MnO2 electrodes were fabricated and applied for investigating the effect of crystal structure on electro-oxidation treatment of N,N-dimethylacetamide (DMAC) containing wastewater. The prepared MnO2 electrodes were characterized by scanning electron microscopy and X-ray diffraction, suggesting that different crystal structures of MnO2 electrodes with the same morphology of stacking-needle structure were successfully prepared. The electrochemical performances, including removal efficiencies of DMAC, chemical oxygen demand (COD) and total nitrogen (TN), and energy consumption, were compared between different MnO2 electrodes. Results indicated that beta-MnO2 electrode presented the excellent electrochemical activity, and could remove 93% DMAC, 62% COD, and 78.9% TN, which was much higher than that of alpha- and gamma-MnO2; moreover, energy consumptions of 11.3, 9.7, and 10.5 kWh/m(3) were calculated for alpha-, beta-, and gamma-MnO2, respectively. Additionally, the oxidation mechanism of the MnO2 electrodes was presented, indicating that DMAC was mainly oxidized by hydroxyl radical through reactions of hydroxylation, demethylation, and deamination, and electrode characteristics of specific surface area, oxygen evolution potential, and hydroxyl radical production were the key factors for degrading DMAC on MnO2 electrodes. Finally, an actual DMAC containing wastewater was applied for testing the electrochemical performance of the three electrodes, and beta-MnO2 electrode was verified as the suitable electrode for potential application which achieved removal efficiencies of 100%, 64.5%, and 73% for DMAC, COD, and TN, respectively, after system optimization.