Curable adhesive films, primers for adhesion of curable adhesive films, and adhesive systems comprising adhesive films and primers are provided. In some embodiments, an adhesive system comprises: I) a curable adhesive free-standing film comprising a blend of a) a first film-forming polymer or oligomer; b) a first species comprising first unsaturated free-radically polymerizable groups, which may be a) or a species other than a); and c) a first transition metal cation; and II) a primer for adhesion of a curable adhesive free-standing film to a first substrate comprising an oxidizing agent. In some embodiments, an adhesive system comprises: I) a curable adhesive free-standing film comprising an outer surface bearing embossed air bleed channels capable of aiding in escape of air during application of the outer surface to a primed substrate; and II) a primer comprising components that initiate cure of the curable adhesive free-standing film.