Abstract: Biocaproate production using cost-effective wastes via anaerobic fermentation becomes a research hot topic due to resource shortage. However, low productivity of caproate limits its wide application in industry. Recent advances of biocaproate production via anaerobic fermentation and the application of cost-effective substrates are reviewed. Clostridium kluyveri is the most common strain used for caproate production, where ethanol, acetate, and butyrate are used as substrates for caproate biosynthesis through two reverse β oxidation cycles to achieve chain elongation. Coculture fermentation, regulation of key environmental factors (electron donor and acceptor concentrations) and alleviation of the inhibitory effects are important methods for improving caproate production. The application of cost-effective substrates reduces production cost, which becomes trends in the future. Food waste is an ideal substrate for caproate production due to its high energy density and productivity.