Cyanostar, a pentagonal macrocyclic compound with an electropositive cavity, binds anions with CH-based hydrogen bonding. The large size of the cyanostar's cavity along with its planarity favor formation of 2:1 sandwich complexes with larger anions, like perchlorate, ClO4-, relative to the smaller chloride. We also show that cyanostar is selective for ClO4- over the bulky salicylate anions by using NMR titration studies to measure affinity. The performance of this novel macrocycle as an anion ionophore in membrane ion sensors was evaluated. The cyanostar-based electrodes demonstrated a Nernstian response toward perchlorate with selectivity patterns distinctly different from the normal Hofmeister series. Different membrane compositions were explored to identify the optimum concentrations of the ionophore, plasticizer, and lipophilic additive that give rise to the best perchlorate selectivity. Changing the concentration of the lipophilic additive tridodecylmethylammonium chloride was found to impact the selectivity pattern and the analytical dynamic range of the electrodes. The high selectivity of the cyanostar sensors and their detection limit could enable the determination of ClO4- in contaminated environmental samples. This novel class of macrocycle provides a suitable scaffold for designing various anion-selective ionophores by altering the size of the central cavity and its functionalization.