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Disclosed herein is a method of preparing a 188 Retricarbonyl complex for radiopharmaceutical use and of preparing a precursor thereof, and a contrast agent using the same. Particularly, this invention provides a method of preparing a 188 Re-tricarbonyl precursor by reacting perrhenate with borane·ammonia (BH 3 ·NH 3 ), potassium boranocarbonate (K 2 [H 3 BCO 2 ]) and phosphate in the presence of borohydride exchange resin as a reducing agent, and a method of preparing a 188 Re-tricarbonyl complex by reacting the 188 Re-tricarbonyl precursor with a ligand. According to the method of this invention, the borohydride exchange resin is used as a reducing agent and as an anion scavenger, thereby obtaining the 188 Re-tricarbonyl precursor and complex having high radiolabeling yield and high purity. In addition, the 188 Re-tricarbonyl complex can be used as a contrast agent having excellent plasma stability.