Heterogeneous photo-Fenton system is widely studied as a very promising water treatment technology. However, there are still some challenges, such as the recovery of solid catalysts, weak photo-Fenton activity at neutral pH and unclear mechanism of photo-assisted Fenton. Here, we demonstrated that hydrothermal synthesized pyrrhotite (SP) was a visible light photo-Fenton catalyst with excellent magnetic recovery performance toward the degradation of organic pollutants at neutral pH. The catalytic degradation performance of SP was 7.5 and 10 times that of natural pyrrhotite (NP) and commercial FeS (com-FeS), respectively. We found that the acid-base buffer function of SP composite was responsible for the photo-Fenton activity at neutral pH. Furthermore, we show that absence of atoms in SP, the formation of vacancies, are responsible for the excellent activity. Overall, this work provide new insight toward the understand of photo assisted Fenton mechanisms at neutral pH.