A triazolium-anthracenyl calix[4]arene conjugate (L) was synthesized by methylating the precursor triazole derivative and then characterized. The potential of the cationic L to differentiate nucleoside triphosphates (NTPs) from their mono- and diphosphates was demonstrated. Due to its unique combination of arms with the calix-platform, a fluorescence enhancement was observed for L with all the NTPs, whereas there is no report with such enhancement being exhibited in case of all the NTPs. This has been supported by the aggregation of L observed from microscopy. Selectivity of L towards NTPs over other phosphates was a result of specific weak interactions, namely, ion-ion, hydrogen bonding and π·π, present in the 1:2 complex of L and NTPs (based on ESI MS), which were absent in their congener-phosphates as delineated by NMR and computational studies. Thus, L stands as a unique receptor for NTPs.