A new series of dinuclear anthracene-containing alkynylplatinum(II) terpyridine complexes exhibited intriguing photo-modulated self-assembly behaviors in solutions. Facilitated by Pt⋯Pt, π–π stacking and hydrophobic interactions, supramolecular assemblies have been formed in their DMSO solutions, featuring interesting spectroscopic responses accompanied by drastic color changes upon varying temperature, and distinct supramolecular nanostructures. Interestingly, these complexes can undergo photooxygenation upon UV excitation, which has been shown to alter their self-assembly behaviors, as revealed by the corresponding electron microscopic and DLS studies before and after photoirradiation.