Two zinc(ii) phthalocyanines substituted with two and four permethylated β-cyclodextrin moieties at the α positions have been synthesised and immobilised on the surface of adamantane-modified silica nanoparticles through host-guest interactions. These molecular and supramolecular systems can catalyse the photooxygenation of 1-naphthol and 2-furoic acid in organic and aqueous media with high conversion efficiency and reaction yield, and photodegradation of 2-chlorophenol in water. Having a higher photostability and recyclability, the supramolecular nanosystems are particularly promising for these photocatalytic applications.