Spectrophotometry and pH measurements were used to study the non-substituted and ortho-substituted calix[4]resorcinarene-mediated transport of Cu(II) and Co(III) complexes with diamine and amino acids from an aqueous source phase to an aqueous receiving phase through a bulky chloroformic membrane. The non-substituted derivative was found to extract complex cations as the anionic ionophore, exchanging protons for the complex across the phase boundary. That is why the reextraction is not effective without acidifying of the receiving phase. The ortho-substituted calix[4]resorcinarenes extract complexes in the form of ionic pairs, which in turn promote their reextraction into receiving phase.