A facile and universal oxygen-tolerant, capillary microfluidic-derived, controlled radical polymerization for surface structuring (gradient and patterned polymer brushes) is reported. A syringe pump and a filter paper sheet are used as capillary microfluidic to supply the reaction solution (monomer, solvent, and ligand) to a sandwich-shaped setup by placing a flat copper plate onto an ATRP initiator-modified substrate and resulting in gradient polymer brush formation with controlled thickness, steepness, and grafting area, polymers are showing the high chain-end fidelity. Two different polymer brushes (binary polymer brushes) can be simultaneously grown from both ends of the initiator modified substrate by using this method, which can be used to study the interfacial properties of different polymer brushes.