Due to the rapid development of the modern chemical industry, a large amount of chlorophenol pollutants remain in the environment. It poses a serious threat to the ecological environment and human health. Advanced oxidation technologies (AOPs) have the characteristics of mild reaction conditions and strong oxidation capacity, and are currently recognized as safe and effective pollutant treatment technologies. In this study, natural lead-rich biochar materials were used to activate sodium persulfate to degrade 2,4-dichlorophenol, and natural lead-rich biochar modified TiO2 photocatalytically degraded 2,4-dichlorophenol. Then, using natural lead-rich metal biochar/TiO2 material, photocatalysis combined with active sodium persulfate to degrade 2,4-dichlorophenol. The experimental results show that the combination of photocatalysis and activated sodium persulfate reaction can completely degrade 100 mg/L 2,4-dichlorophenol under UV light for 3 h, and the degradation efficiency is much higher than the sum of the two separate reactions. Quenching experiments show that SO4- • radicals play the most important role in the three free radicals (SO4- •, •OH and •O2- ) in the advanced oxidation combination system. Finally, the reaction mechanism of the two advanced oxidation combined systems are speculated.