The synergism between mechanical friction and corrosion may lead to an acceleration of the degradation of materials in sliding contacts exposed to the environment. Electrochemical measurements and sliding tests are proposed as a protocol suitable to decouple the material losses originating from the active material and the passive film, and to identify their electrochemical or mechanical nature. The corrosion resistance of a material, its ability to react onto chemical or mechanical attack, its susceptibility to tribocorrosion and the effect of a passive surface film on the coefficient of friction are evaluated. The proposed tribo-electrochemical protocol allows to evaluate the potential and risks of applying newly developed materials in sliding contacts, and to support the selection and implementation of materials in industry in applications where corrosion and wear are potential degradation processes. This protocol extends the existing Standard Guide ASTM G 119-04 'Determining Synergism between wear and Corrosion' for passivating metallic materials. Copyright (C) 2009 John Wiley & Sons, Ltd.