This paper introduces a set of new concepts related to the macromolecular design and to the practice in the realm of lamination by photografting, with experimental studies of the synthesis, structure, and performance of various systems, including valence bond adhesion of the organic polymeric materials, hyperbranched macromolecules rooted to the surface of organic substrates, macromolecular networks rooted on and bridged between two organic substrates, and a synthetic route combining primary and secondary photografting processes for the preparation of supermolecular architectures. In successful photolamination experiments based on these ideas, hyperbranched macromolecules of large size (10-20 mu m) were obtained after initiation with aromatic ketones, which undergo a photoreduction reaction. A range of different organic polymeric films have been laminated. T-peel tests show most of the laminates broke inside the substrates and not at the interface between adhesive and substrate.