NOVELTY - Forming multilayer polymacromer composition involves (a1) functionalizing substrate with primer surface group; (b1) covalently linking to primer surface group, a linker having photocleavable functionality and click moiety terminus; (c1) forming monomolecular layer by contacting terminus of the linker with heterobifunctional macromolecule having polymer backbone, click moiety terminus and protected second click moiety terminus; (d1) deprotecting protected second terminus to form functionalized monomolecular layer; and (e1) contacting functionalized layer with second macromolecule.    USE - For generating a multilayer polymacromer composition (claimed) useful in energy conversion storage devices, solar cell fabrication, adhesion, self-cleaning surfaces, drug delivery vehicles, and stem cell scaffolds.    ADVANTAGE - The method yields greater than 90 (preferably greater than 95)% of the multilayer polymacromer composition; and forms monomolecular layer with efficiency of greater than 90 (preferably greater than 95)%. The method provides utilizes click chemistry techniques which enable one to elaborate the dendrimer without disturbing other functional groups present and also ensures high yielding steps at each iteration of growth.    DETAILED DESCRIPTION - Generating a multilayer polymacromer composition, involves: (a1) functionalizing a substrate with a primer surface group to form a functionalized substrate layer; (b1) covalently linking a linker to the primer surface group, where the linker comprises a photocleavable functionality and a click moiety terminus; (c1) forming a monomolecular layer by contacting the click moiety terminus of the linker with a first heterobifunctional macromolecule comprising a polymer backbone, a first click moiety terminus and a protected second click moiety terminus; (d1) deprotecting the protected second click moiety terminus to form a functionalized monomolecular layer; and (e1) forming a second monomolecular layer by contacting the functionalized monomolecular layer with a second heterobifunctional macromolecule comprising a polymer backbone, a first click moiety terminus and a protected second click moiety terminus, or a first heterotrifunctional branch comprising a first click moiety group and at least two protected second click moiety groups. An INDEPENDENT CLAIM is included for a multilayer polymacromer composition (c2) comprising: a first terminus comprising a nitrophenyl functionality, and n-layers, where each layer comprises a poly(tert-butyl acrylate) macromolecule, and n is an integer between 1-100.