The invention discloses an environment-friendly composite stainless steel cleaning agent and a preparation method thereof. The environment-friendly composite stainless steel cleaning agent comprises organic acid citric acid, ammonium hydroxide, zinc salt, a chelating agent, a fluoride additive, a surface active agent, a defoaming agent and water. The zinc salt is zinc sulfate or zinc dihydrogen phosphate. The chelating agent is hydroxy carboxylic acid matter. The fluoride additive is NaF or Na2SiF6 or NH4HF2. The surface active agent is polyoxyethylene ether matter. When the cleaning agent isprepared, firstly, the zinc salt is added into water, and the zinc salt is completely dissolved uniformly; and the citric acid is added under the proper temperature, after stirring is carried out to complete dissolution, the ammonium hydroxide is added to adjust the PH, the fluoride additive, the chelating agent, the surface active agent and the defoaming agent are added sequentially, stirring iscarried out to obtain a solution homogeneous phase, and preparation of the environment-friendly composite cleaning agent is completed. The organic acid citric acid is used as main acid of the environment-friendly composite stainless steel cleaning agent, pollution to the environment is small, corrosion to equipment is small, waste liquid is easily treated, and three procedures including stainlesssteel oil removal, rust removal and passivation can be completed in one step during cleaning.