A novel coupled system using Co–Ti O2 was successfully designed which combined two different heterogeneous advanced oxidation processes, sulfate radical based Fenton-like reaction(SR-Fenton) and visible light photocatalysis(Vis-Photo), for degradation of organic contaminants. The synergistic effect of SR-Fenton and Vis-Photo was observed through comparative tests of 50 mg/L Rhodamine B(Rh B) degradation and TOC removal. The Rhodamine B degradation rate and TOC removal were 100% and 68.1% using the SR-Fenton/Vis-Photo combined process under ambient conditions, respectively. Moreover, based on XRD, XPS and UV-DRS characterization, it can be deduced that tricobalt tetroxide located on the surface of the catalyst is the SR-Fenton active site, and cobalt ion implanted in the Ti O2 lattice is the reason for the visible light photocatalytic activity of Co–Ti O2. Finally, the effects of the calcination temperature and cobalt concentration on the synergistic performance were also investigated and a possible mechanism for the synergistic system was proposed. This coupled system exhibited excellent catalytic stability and reusability,and almost no dissolution of Co2+was found.