Titanium dioxide is nowadays a protagonist in advanced lithographic techniques. When TiO2 is irradiated by UV light, organic molecules placed either on its surface (direct photocatalysis) or in its proximity (remote photocatalysis) are swiftly degraded [1]. Photocatalytic lithography is a versatile approach for the patterning of self-assembled monolayers, but it has never been applied in the field of polymer brushes. Polymer brushes, stretched arrays of polymer chains chemically attached to a surface, are powerful tools for surface engineering, in fields ranging from biochemistry to electronics. In the “grafting-from” approach, a surface-immobilized initiator allows the growth of polymer brushes directly from the surface: if the initiator layer is patterned, patterned brushes will be obtained. In this work, the properties of titanium dioxide is used, for the first time, in initiator patterning. Compared to classic photolithography, photocatalytic lithography allows the patterning of polymer brushes (with micrometer resolution) with unprecedented ease: it does not require resists and intense UV sources. Here, initiators of polymerization were grafted on different substrates, patterned using direct and remote photocatalytic lithography and amplified into polymer brushes. The brushes themselves were found to be photopatternable: different initiators display different sensitivity to UV irradiation, making tunable the degrafting process. The brush-free surfaces could be refilled with fresh initiator to restart polymerization with different monomers, thus obtaining binary brushes. Photocatalytic lithography can thus pave the way to easy making of functional surfaces, with potential applications ranging from sensor technology (e.g. molecular recognition) to microfluidics. [1] G. Soliveri, V. Pifferi, G. Panzarasa, S. Ardizzone, G. Cappelletti, D. Meroni, K. Sparnacci, L. Falciola, Analyst 2015, 140, 1486–1494.