The functionalization of amphiphilic polymer co-networks with light-responsive spiropyran and spirooxazine derivatives leads to a new type of light-responsive materials. The material consisting of hydrophilic nano-channels shows desirable properties such as light-responsive permeability changes of aqueous caffeine solutions, an exceptional repeatability of the photochromism, and tunable basic permeability rates. The versatility of the system is demonstrated by using different functionalization routes such as copolymerization of light-responsive monomers or crosslinker as well as postmodification of the preformed amphiphilic network. Moreover, light-responsive spirobenzopyran and novel spirooxazine derivatives are synthesized, which changes the properties of the light-responsive membranes after inclusion into the amphiphilic co-networks. Finally, the permeability of the delivery membrane can be tailored to match the properties of porcine skin, an in vitro model of human neonatal skin. One possible application might be the use of the light-responsive membranes as key-unit of a transdermal caffeine-delivery system for preterm neonates.