Designing molecular receptors featuring the bowl-shaped sumanene motif and dedicated to the detection of metal cations constitute an emerging field of applied supramolecular chemistry of this buckybowl. In this work, we achieved the successful synthesis of a new class of sumanene-based receptors, which key-structural feature was the presence of two or three sumanene units linked via a 1,2,3-triazole skeletons generated in the 1,3-dipolar cycloaddition reaction (click chemistry approach). The designed compounds were found to recognize metal cations both in solution (spectrofluorometric studies) as well as in heterogeneous system (polymeric membrane of potentiometric sensors). In terms of optical studies in solution, title molecules featured fluorescence quenching behaviours upon addition of metal cations, with Stern-Volmer constant values at the level of 106 M−1. The spectrofluorometric and potentiometric results were generally in a good agreement, revealing the preferential binding of lithium (Li+), caesium (Cs+) or copper(II) (Cu2+) cations depending on the receptor structure. This work also includes the density functional theory (DFT) computational studies on the structure and receptor properties of the title molecules. The results indicated attractive possibilities for the design of novel organic materials based on sumanene scaffold and toward tuning the recognition properties of the sumanene based receptors for different metal cations.