Novel composite coatings were fabricated on 6061 aluminum alloy substrates by two steps combining micro-arc oxidation (MAO) plus electroless copper plating (Cu). Different MAO + Cu composite coatings were compared. Cu continuously and evenly covered an aluminum oxide surface during processing thus changing the surface topography. The adhesion of MAO + Cu composite coating was tested by the pull-out method. The best adhesion strength of the composite coating can reach industrial requirements. The effects of the composite coatings on friction were investigated using a ball-on-disc test method. It is found that copper in composite coatings plays a lubricating effect during the wear process under dry sliding. Furthermore, the mechanisms by which the observed advantages were produced are discussed.