The invention provides a method for extracting and separating silver by a double-aqueous phase system. The method comprises the following steps: carrying out mixed extraction on a to-be-separated silver-bearing solution, the double-aqueous phase system and a complexing agent, and carrying out stewing layering, so that silver ions are separated and enter an organic phase, wherein the double-aqueous phase system comprises C2-C3 alcohol, water and a salting-out agent, and the complexing agent is selected from one or more of potassium thiocyanate and hexadecyl trimethyl ammonium bromide. According to the method provided by the invention, the mixed exaction of silver is realized by the double-aqueous phase system and the complexing agent, that is, in the double-aqueous phase system formed by the alcohol, water and the salting-out agent, an ionic associate formed by the extracted silver and the complexing agent, the extraction effect is good, and the extraction rate is high. Compared with the traditional organic solvent extraction method, the method has the advantages of small interference, quick separation, separated phase cleaning and good extraction effect, and meanwhile, the use of toxic reagents is used, thereby being environmentally friendly.