In the present work new naphthalene appended calix[4]arene (NAC4) i.e. 5,11,17,23-tetra-tert-butyl-25,27-di((2-amido(1-naphthlene)ethyl)-26,28-dihydroxy calix[4]arene (6) was designed and successfully synthesized. NAC4 was characterized by 1HNMR and FTIR. To explore the complexation behavior and fluorescence response of NAC4, UV-visible and fluorescence studies were carried out with series of metal ions and anions that include solvatochromic effect, ion-ligand response and interference on absorption and fluorescence spectra. Results show that the NAC4 is highly Cu2+ and I−selective. The ligand ion interaction follow photoinduced electron transfer (PET) mechanism. The stiochiomatric ratio of ion-ligand was calculated as 1:1 by using Job’s plot method and binding constant Ka values were calculated by using Benesi-Hildebrand equation as 1×103 and 8×102 M−1 with detection limit of 1.05×10−5 and 4.0×10−5 M for Cu2+ and I− respectively. [Figure not available: see fulltext.]