Cu⁰-mediated surface-initiated ATRP (Cu⁰ SI-ATRP) emerges as a versatile, oxygen-tolerant process to functionalize three-dimensional (3D), microporous supports forming single and multiple polymer-brush gradients with a fully tunable composition. When polymerization mixtures are dispensed on a Cu⁰-coated plate, this acts as oxygen scavenger and source of active catalyst. In the presence of an ATRP initiator-bearing microporous elastomer placed in contact with the metallic plate, the reaction solution infiltrates by capillarity through the support, simultaneously triggering the controlled growth of polymer brushes. The polymer grafting process proceeds with kinetics that are determined by the progressive infiltration of the reaction solution within the microporous support and by the continuous diffusion of catalyst regenerated at the Cu⁰ surface. The combination of these effects enables the accessible generation of 3D polymer-brush gradients extending across the microporous scaffolds used as supports, finally providing materials with a continuous variation of interfacial composition and properties.