Organic films have been grafted to glassy carbon surfaces by the photolysis of arylazides. Atomic force microscopy and electrochemical measurements reveal that the films are loosely packed. The methodology was expanded to prepare two-component thin films incorporating either a reactive tether species and a nonreactive background film or two different reactive tethers. Strategies were developed to generate both continuous mixed films and surfaces presenting patterns of two components. For patterning, the arylazide derivative was grafted onto previously modified glassy carbon surfaces. In this case, the first modification step is not limited to photografting, which increases the scope of the methods. For all grafted surfaces, the reactivity of tether species was confirmed by coupling electroactive targets to the tethers, followed by electrochemical monitoring. The ease of preparing surfaces with spatially controlled functionality offers promise for the design of sensing platforms on graphitic carbon substrates.