A readily available chromionophore 5,11,17,23-tetra-tert-butyl-25,27-bis(hydrazidecarbonylmethoxy)-26,28-dihydroxycalixarene (HCC4) was employed as a chromogenic sensing probe selective for Pb(II) and Cr2O7 (2-) ions among a series of various ions such as Li(I), Na(I), K(I), Rb(I), Ba(II), Sr(II), Al(III), Cd(II), Co(II), Cu(II), Hg(II), Ni(II), Pb(II) and Zn(II) as well as Cr2O7 (2-), CH3CO2 (-), Br-, Cl-, F-, I-, ClO4 (-) and NO3 (-) that have been examined by UV-visible and fluorescence spectroscopic techniques. The HCC4 in DCM-MeCN system forms 2:1 (ligand-metal) complex with Pb(II). It also shows 2:1 stoichiometry with Cr2O7 (2-). The complexation phenomenon has been confirmed by FTIR spectroscopy that favors the selective nature of HCC4 with Pb(II) and Cr2O7 (2-). Thermal gravimetric analysis (TGA) also supports its utility in drastic conditions.