The article depicts a detailed study regarding copper selective chemosensing and complexation nature of 5,11,17,23-tetrakis[(N,N-diphenylamino)methyl]-25,26,27,28-tetrahydroxycalixarene (PAC4). Its photophysical characteristics in various solvents of different polarities along with the influence of acid and base on its spectral properties in these solvents are also discussed. The complexation affinity of PAC4 with regard to its latent applications as Cu(II) selective colorimetric and fluorescent sensor among the selected series of various cations such as Li(I), Na(I), K(I), Rb(I), Ba(II), Sr(II), Al(III), Fe(III), Cd(II), Co(II), Hg(II), Mn(II), Ni(II), Pb(II) and Zn(II) was examined by UV-visible and fluorescence emission spectroscopy in dichloromethane:acetonitrile (DCM:MeCN) solvent system. In addition, the process of complexation has been investigated through Job's plot and it has been observed that the complex between PAC4 and Cu(II) is formed in 1:1 stoichiometric ratio. The complex formation between PAC4 and Cu(II) has also been confirmed by FT-IR spectroscopy and thermal gravimetric analysis (TGA). (C) 2012 Elsevier B.V. All rights reserved.