The invention discloses an environment-friendly copper and copper alloy pickling agent and a copper and copper alloy silver-plating pretreatment method. The pickling agent is prepared from the following ingredients in percentage by mass: 21.5-44.0% of sulfuric acid, 2.5-15.5% of phytic acid, 2.5-10% of sodium nitrate, 0.5-2.0% of dispersing agent and the balance of water. The environment-friendly pickling agent is clean and environment-friendly, has no solvent volatilization, cannot generate acid mist during cleaning, has low pollution, can create a clean environment for pretreatment process, has high copper and copper alloy cleaning quality, and can prevent parts from being over-etched, realizes cleaning of silver-plating pretreatment of copper, copper-like and copper alloy used for high-voltage switches, can improve the operation environment, can protect the health of staffs, can be used repeatedly during cleaning, has the using period which is more 2-3 times than that of the traditional pickling acid, can greatly reduce the cleaning cost, has remarkable comprehensive benefit and is suitable for popularization and application.