A novel voltammetric method for the sensitive determination of ethylenediaminetetraacetic acid (EDTA) was developed based on a graphene oxide (GO) modified electrode. In acetate buffer solution, GO showed a voltammetric response composed of a sharp anodic peak and a weak cathodic peak. When EDTA was present in the solution, the voltammetric response of GO was suppressed. Under optimum conditions, the response of the GO‐modified electrode was inversely proportional to the concentration of EDTA from 6.0×10−7 to 1.0×10−4 mol/L. Using such a GO‐based voltammetry, the effective photoelectrocatalytic degradation of EDTA over a TiO2 film electrode was evaluated and some influencing factors were investigated.