A method for electroless coating of substrates by applying an activating coat of polyelectrolyte or salt with a first aqueous composition; rinsing the activating coat such that the activating coat not being entirely removed; contacting and coating of the activated surfaces that have remained after rinsing with an aqueous composition in the form of a solution, emulsion or suspension, to form an organic secondary coat; and drying. The activating coat is a solution, emulsion or suspension containing a anionic polyelectrolyte or at least one anionic salt in solution in water. The aqueous composition forming the secondary coat has constituents which can be precipitated, deposited or salted out and which are anionically, zwitterionically, sterically or cationically stabilized. The dry film formed in the process, comprising the activating coat and the secondary coat, has a thickness of at least 1 μm.