A heterogeneous supramolecular catalytic system for multicomponent aldol-'click' reactions is reported. The copper(I) metallohydrogel functionalized with a phenyltriazole fragment was able to catalyze the multicomponent reaction between phenylacetylene, p-nitrobenzaldehyde, and an azide containing a ketone moiety, obtaining the corresponding aldol products in good yields. A possible mechanistic pathway responsible for this unexpected catalytic behavior has been proposed.