Electrochemical dechlorination experiments based on the principle of galvanic cell were carried out on reinforced concrete with different water-cement ratios. The evolution of electrochemical parameters of reinforced concrete with different water-cement ratios over time was studied. The results show that the higher the water-cement ratio, the more negative the anodic operating potential at the initial stage of dechlorination, the larger the loop current, and the higher the dechlorination efficiency. The higher the water-cement ratio, the more obvious the positive shift of corrosion potential of the rebar after dechlorination, the greater the increase of polarization resistance, and the smaller the increase of OH^- concentration. After dechlorination, the contents of C-S-H gel and Friedel’s salt in concrete slightly decrease, while the content of Ca(OH)2 slightly increases, and a small amount of AFt and C-S-H gel decomposes.