Self-assembled thin films of 3,4,9, 10-perylenediiinides (PDIs) containing up to 50 PDI layers were grown on quartz slides using the zirconium phosphonate technique. When the films were immersed in aqueous solutions of the sodium dithionite reducing agent, in situ reduction of the dye was observed, generating a purple film containing PDI radical anions. The PDI radical anions formed within the films were rather stable, persisting for several minutes in the presence of atmospheric oxygen. Atomic force microscopy (AFM) images showed that the film surface was rather smooth and pinhole-free.