As there are some disadvantages in the measurement of redox potential (ORP) of sediment using conventional methods, we proposed a method based on the microbial fuel cell technology for evaluating the redox condition of sediment. Higher rate of electricity recovery by the microbial fuel cell technology was obtained from the sediment that had lower ORP, higher reduction capacity, and higher content of labile structural organic matter. Strong correlations between these parameters were found, ensuring that our method can be used to evaluate the ORP of sediment. Furthermore, our method makes it possible to continuously measure the redox potential of sediment in long period comparing with conventional methods.