The production and accumulation of propionic acid affect significantly anaerobic wastewater treatment system, but the reasons are not approached until now. Based on the results of continuous-flow tests and the analysis of biochemistry and ecology, two mechanisms of producing propionic acid have been put forward. It is demonstrated that the reasons of propionic acid production and accumulation are not caused by higher hydrogen partial pressure. The combination of specific pH value and ORP is the ecological factor affecting propionic acid production, and the equilibrium regulation of NADH/NAD+ ratio in cells is the physiological factor. Meanwhile, it is put forward that using the two-phase anaerobic treatment process and the ethanol type fermentation in anaerobic reactor to avoid propionic acid accumulation are efficient methods.