Methods of making a multilayer optical film are described. In one embodiment, the method comprises providing a multilayer optical film and disposing onto the multilayer optical film a plurality of layers deposited by layer-by-layer self-assembly of nanoparticles, polymers, and combinations thereof. The multilayer optical film typically comprises a plurality of alternating polymeric layers of a low refractive index layer and a high refractive index layer that reflects at least one bandwidth of electromagnetic radiation ranging from ultraviolet to near infrared. Multilayer optical film articles are described comprising a plurality of layers disposed onto the multilayer optical film, wherein the plurality of layers comprises layer-by-layer self-assembled nanoparticles, polymers, and combinations thereof. The multilayer optical films are suitable for various uses including reflective polarizers for optical displays such as LCDs or LEDs, architectural film applications, window film applications, and solar power concentrating mirrors.