A Pd on Ni-B (Pd/Ni-B) bimetallic catalyst was prepared and tested in the hydrodechlorination (HDC) of 4-chlorophenol (4-CP). The catalysts were synthesized by replacement method and treated at different temperatures (298-673 K). The results showed that the one treated at 473 K could achieve complete dechlorination of 200 ppm 4-CP under the pH = 8 within 30 min and keep the high activity in the first four recycles. The introducing of Pd greatly promoted the catalytic HDC efficiency of Ni-B, and the high dispersion of Pd species ensured the high activity of Pd/Ni-B catalysts. The catalytic HDC reaction of 4-CP followed the pseudo-first-order dynamics and the kinetic data was obtained.