The discharge of hydroquinone (HQ), an important chemical raw material, to natural waters poses different ecological threats to aquatic organisms. In this study, we investigated the removal performance of traditional and modified microelectrolysis methods in aqueous solutions. The traditional microelectrolysis packing was modified by adding manganese (Mn), zinc (Zn), and copper (Cu) powder as additives. The factors affecting the removal performance of HQ, such as catalytic metal type, mass fraction of additive, reaction time, and initial pH, were examined. The results showed that the Mn modified packing exhibited the best performance compared to Zn and Cu powder. The removal rate of HQ using Mn modified packing can reach 94% after 4 h. In addition, 9% of Mn packing has a higher removal rate than other mass fractions. The acidic solution pH shows a more favorable degradation than a neutral and alkaline solution. The intermediates of HQ degradation by modified microelectrolysis were identified and then the pathway of HQ degradation was proposed. Our result indicates that Mn as catalytic metal holds promising potential to enhance HQ removal in water using the microelectrolysis method.