The biodegradable calcium/phosphate coating on the surface of the magnesium alloy AZ31B was prepared by atmospheric plasma spraying. The phase compositions and crystallinity of the coating were quantitative investigated by XRD, and the microscopic morphology and elemental composition of the coating before and after immersion in the simulated body fluid (SBF) were investigated by SEM and EDS. The degradability of magnesium alloy with calcium/phosphorus coating in SBF solution were studied according to the pH value and the degradation rate of the coating. The results show that the high density calcium/phosphate coating is closely integrated with the magnesium alloy substrate. The coating is composed of HA with difficult degradation and Ca3(PO4)2, Ca4P2O9 and CaO with easy degradation, and the crystallinity of HA in the coating is 49.3%. In addition, the study of biodegradation shows that the pH value and the degradation rate of the calcium/phosphorus coating in SBF are less than that of magnesium alloy, and the smaller change magnitude makes the coating material’s degradation be controlled in a stable range.