The conditions for the treatment of high phosphorus pharmaceutical wastewater using chemical precipitation were determined to achieve high efficiency on the removal of total phosphorus (TP). The key factors affecting the TP removal efficiencies of four metal salts (FeCl3, AlCl3, MgCl2, and CaCl2), such as molar ratio, initial wastewater pH, and reaction time, were investigated. The optimal metal mole ratios of FeCl3, AlCl3P, MgCl2, and CaCl2 for the TP removal were 1.8:1, 1.8:1, 1.6:1, and 1.6:1 in the initial pH range, respectively. The TP removal efficiencies obtained by FeCl3, AlCl3, MgCl2, and CaCl2 were 99.8%, 98.3%, 96.9%, and 99.2% at the optimal mole ratio and pH conditions with 30min reaction time, respectively. FeCl3 and AlCl3 had better removal performance on COD, wherein the removal rates of COD by FeCl3 and AlCl3 were 38.6% and 27.6%, respectively. FeCl3 and CaCl2 were selected for the combined process of removing TP and overcoming the aforementioned problem. The final effluent quality was better than the one only used on one of the four metal salts, in which the removal rates of TP and COD were as high as 99.8% and 46.9%, respectively. The combined process with FeCl3 and CaCl2 was an effective method for the pretreatment of high phosphorus pharmaceutical wastewater to reduce the processing cost and to decrease the chemical oxygen demand (COD) and TP.