New fixing agents were prepared by the reaction of thiocyanate and acid salt of inorganic compound such as sodium hydrogen sulfite, sodium hydrogen carbonate, and sodium hydrogen sulfate in the presence of acid or salt. The reaction was carried out between 65 and 75°C for about 2.5 hours. The agents were stable to light and humidity, and the hygroscopicity of the agents was about 20-30% less than that of thiocyanate. The fixing property of agents was compared with thiosulfate. The fixing time of the agents was much shorter than that of thiosulfate. Among these agents, the clearing time was reduced in the order of nNH4SCN·NaHSO₄4SCN·NaHSO₃4SCN·NaHCO₃. The agents were found to be useful as a rapid fixing agent for silver halide emulsion.