Water soluble symmetrically tetrasubstituted calix[4]arene derivatives cone-5,11,17,23-tetrakis(2-pyridylmethylamino)-25,26,27,28-tetrakis(carboxymethoxy)calix-[4]arene 4a, cone-5,11,17,23-tetrakis(3-pyridylmethylamino)-25,26,27,28-tetrakis(car-boxymethoxy)calix[4]arene 4b, cone-5,11,17,23-tetrakis(4-pyridylmethylamino)-25,26, 27,28-tetrakis(carboxymethoxy)calix[4]arene 4c, and cone-5,11,17,23-tetraamino-25,26, 27,28-tetrakis(carboxymethoxy)calix[4]arene 6 and their precursors were synthesized and characterized. The upper rim nitro- and imino-substituted precursors of these compounds, their crystal structures as well as crystal structure of copper(II) complex of cone-5,11, 17,23-tetranitro-25,26,27,28-tetrakis(carboxymethoxy)calix[4]arene 5 are also reported.