For nearly two centuries, researchers have sought novel methods to increase light transmission in optical systems, as well as to eliminate unwanted reflections and glare. Antireflection coatings and surfaces have enabled the increasing performance demands of optical components fabricated from glass-based optical materials. With the current trend of technology moving towards optically transparent polymeric media and coatings, the need for antireflection technology and environmentally benign processing methods for polymeric materials independent of shape or size has become quite apparent. We describe an economical, aqueous-based process controlled at the molecular level that simultaneously coats all surfaces of almost any material. Systematically designed nanoporous polymer films are used, which are suitable for optical applications operating at both visible and near-infrared wavelengths. These high-efficiency anti-reflection coatings are created from phase-separated polyelectrolyte multilayer films that undergo a reversible pH-induced swelling transition. Furthermore, such films, easily patterned by an inkjet printing technique, possess potential for pH-responsive biomaterial and membrane applications.