Pd/Ti electrode was prepared on Ti substrate electrode using cyclic voltammetry in hydrochloric acid containing PdCl₂. The electrocatalytic performance toward electrochemical reduction reactivity of 3-chlorobenzoic acid (3-CBA) on Cu, Ag, Ti and Pd/Ti electrodes was investigated by cyclic voltammetry. Compared with Cu, Ag and Ti electrodes, Pd/Ti electrode exhibited a high electrochemical activity for the reduction process of 3-CBA in NaOH solution. In situ FTIR was applied to analyze the electrochemical dechlorination mechanism of 3-CBA systematically. The results showed that 3-CBA was electroreduced to its free radical ion after receiving an electron. Then the 3-CBA free radical took off a chloride ion and produced the benzoic acid free radical. After receiving another electron and a proton, the final product benzoic acid was obtained.