In order to induce adhesion of electroless CuNiP deposition to polyimide (PI) film substrate, surface modification of PI film with an aqueous dispersion of ozone micro–nano bubbles was investigated. The treatment resulted in maximum adhesion strength of 1·14 kN m−1 for a treatment time of 5 min. Structure of the modified PI surface, the PI/plating interface, mechanism for adhesion and laminate properties were analysed. Despite increased adhesion, surface roughness of PI was not notably changed by the ozone induced surface modification. Contact of PI surface with high ozone concentration micro–nano bubbles with sufficient frequency was found to modify the surface with a low total ozone concentration of the aqueous dispersion. Cross-sectional observation of the interface suggested that formation of a thin nanoporous anchor layer on the PI surface was responsible for plating adhesion. This method provides an environment friendly and improved process for plating on PI using low concentration ozone treatment.