The sulfate radical based advanced oxidation process (SR-AOP) is an emerging technology for the degradation of micropollutants with various advantages such as low cost, high efficiency, high availability, high capability, long lifespan, higher reaction rate, and redox potential. This review focuses on the chemistry and catalytic aspects of various activation strategies of persulfate systems. This review discusses the opportunities and challenges of radical based catalysis, including microwave, thermal based radiation, ultrasonication, and ionizing radiation such as γ radiation and electron beam radiation. This review covers the reaction mechanism of sulfate radicals, the parameters influencing the degradation kinetics of different methods of persulfate activation, the influence of hydroxyl radicals in the persulfate system, characteristics, and economic analysis aspects. Nevertheless, knowledge gaps and challenges for achieving maximum efficiency are also explored which track how to work further and implement processes against various pollutants in subsequent research.