We use microcontact printing (μCP) of polyelectrolytes (PEs) onto flat substrates for creating surfaces with regions of negative and positive surface charge. Subsequent incubation of these surfaces with solutions containing hollow PE capsules leads to preferential adsorption of the capsules on regions of opposite charge, while regions of like charge are passivated against adhesion. As well, adsorption of fluorescently labeled PEs is found to be directed toward oppositely charged regions at neutral pH. This approach could lead to novel functional surfaces for combinatorial chemistry or sensor applications and could also be expanded toward cell immobilization.