Efficient elimination of antibacterial activity of halogenated antibiotics by dehalogenation pretreatment is desired for a biochemical treatment process. In this study, crystalline cobalt phosphide nanosheet arrays on a Ti plate (C-CoP/Ti) are fabricated by a simple electrodeposition and phosphorization process. The crystalline structure greatly promotes atomic hydrogen (H*) generation. Moreover, the nanosheet arrays can provide abundant active sites and accelerate electron transfer and mass transport. As a result, the dehalogenation rate of florfenicol (FLO, an emerging organic pollutant) on C-CoP/Ti is 11.1, 2.97, and 13.6 times higher than that on amorphous CoP/Ti, Pd/Ti, and bare Ti, respectively. The C-CoP/Ti electrode achieves 97.4% dehalogenation of FLO (20 mg L-1) within 30 min at -1.2 V (vs Ag/AgCl). Nearly 100% of Cl and 20% of F are broken away within 120 min, showing the highest electrocatalytic defluorination efficiency reported so far. Both experimental results and theoretical calculations reveal that the dehalogenation of FLO on C-CoP/Ti is synergistically accomplished via direct reduction of electron transfer and indirect reduction of H*. This study develops a highly efficient non-noble metal electrode material for dehalogenation of halogenated organic compounds.