Microporous and nanoporous polyelectrolyte multilayer films have been explored as ultrathin coatings for controlled drug release. Ketoprofen and cytochalasin D were successfully loaded into nanoporous films and showed zero-order release kinetics over a period of many days. In addition to homogeneous porous multilayers, heterostructures comprising porous regions stacked alternately with nonporous regions were assembled. The heterostructures behaved as dielectric mirrors, which made it possible to optically monitor the loading process. The effects of varying the number of layers in porous and nonporous regions as well as the pore size on the drug release properties were studied. Nonporous regions in the film had no effect on the release rate or duration of release. The amount of drug released could be tuned by varying the number of layers in the porous regions of films, and the release rate depended on the pore size in the films. Microporous multilayers exhibited a Fickian diffusion of drug that was approximately twice as fast as the corresponding nanoporous films. Finally, cell culture experiments with WT NR6 fibroblasts confirmed that cytochalasin D retained its ability to inhibit mitosis after release from the multilayers.