A unique method for creating polymer nanofibers and spheres on a variety of substrates is described. Cyanoacrylate monomer vapor was collected on a solid surface and polymerized to form nanofibers. Tiny spots of initiator on the surface of a substrate and small monomer droplets in a monomer vapor appear to be required for the growth of the polycyanoacrylate nanofibers. The polycyanoacrylate nanofibers create a network and increase the specific surface area significantly.