•Reduced graphene oxide/Ag composites were embedded into nanosponge architectures.•The composite materials were tested as photocatalysts for dyes degradation.•Synergistic improvement of the catalyst efficiency was assessed.•Reusability of the composite photocatalyst material was tested. Significant activity improvement was achieved by associating graphene oxide-silver composite photocatalysts with cyclodextrin-based nanosponge materials, due to the synergistic effect provided by the supramolecular host abilities of the nanosponge. Three photocatalysts were prepared, fully characterized (FT-IR, ss-NMR, Raman, XRD, SEM, EDX, AFM, ICP, TGA, potentiometric titration), and tested for the oxidative photodegradation of some dyes and phenols, chosen as model organic pollutants. Compared to the unsupported photocatalyst, the nanosponge-based materials showed enhanced performances (being able to carry out the degradation even of dyes which do not react in the presence of the unsupported catalyst), and good recyclability. The activity improvement is attributed to a local concentration effect provided by the nanosponge, able to capture the organic substrate in the proximity of the actual photocatalyst. The results presented herein provide a helpful basis for designing advanced catalytic systems. Display omitted