Resorcin[4]arene-based ligand bearing four heptyl chains at the lower rim of the molecule was prepared and modified by four tetradietoxyphosphoryl groups in the upper rim. The compounds obtained were characterized by NMR spectroscopy and their extractability toward chromium(III) ions was studied. The influence of process parameters such as the pH of aqueous phase, agitation time and also extractant’s structure and concentration on efficiency of Cr(III) ions solvent extraction is presented. The highest yield of Cr(III) solvent extraction was obtained for two-hour agitation time of 5.010−4 M metal solution of pH 5.0 and 5.010−3 M chloroform solution of the tetradietoxyphosphorylated derivative of heptyl-resorcin[4]arene. Under optimal conditions, competitive solvent extraction of Cr(III), Zn(II), and Cd(II) ions was performed and separation factor values were established as 77.0 and 24.9 for Cr(III)/Cd(II) and Cr(III)/Zn(II) ions pairs, respectively. The stoichiometry of formed metal-ligand complexes 1:1 was found by classical slope analysis method.