The invention discloses a collecting agent for flotation of complex and difficult-to-treat copper sulfide silver ore, which is prepared by mixing the following components in percentage by mass: 55 to 75 percent of sulfur nitrogen nitrile ester, 20 to 40 percent of ethionine ester and 5 to 15 percent of polyethylene glycol alkyl ether. The collecting agent disclosed by the invention not only has very strong collecting performance, but also has foamability, so that the cost of a foaming agent can be saved in production; due to the fact that the collecting agent MT-23 is high in capacity, the total consumption of the agent per ton of ore is extremely low; the flotation cost is saved by more than 25% compared with that of an existing agent; the collecting agent is non-toxic, odorless and easy to degrade, belongs to a green and environment-friendly mineral separation collecting agent, and has a wide popularization prospect. By the adoption of the method, the recovery rate of copper and silver can be remarkably increased on the premise that the quality of copper-silver concentrate products is guaranteed, and the method has the advantages of being simple in technological process, stable, reliable, high in applicability, simple in reagent system, small in reagent dosage, convenient to add and the like.