Some composite materials have been prepared, constituted by a cyclodextrin-bis-urethane-based nanosponge matrix in which a reduced graphene oxide/silver nanoparticles photocatalyst has been dispersed. Different chain extenders were employed for designing the nanosponge supports, in such a way as to decorate their hyper-cross-linked structure with diverse functionalities. Moreover, two different strategies were explored to accomplish the silver loading. The obtained systems were successfully tested as catalysts for the photodegradation of emerging pollutants such as model dyes and drugs. Enhancement of the photoactive species performance (up to nine times), due to the synergistic local concentration effect exerted by the nanosponge, could be assessed. Overall, the best performances were shown by polyamine-decorated materials, which were able to promote the degradation of some particularly resistant drugs. Some methodological issues pertaining to data collection are also addressed.