In the present work, a phenomenon of supramolecular solvent formation based on primary amine citrate was presented for the first time. Tetrabutylammonium bromide was investigated as a coacervation agent in an extraction system, and possible interactions responsible for its ability to induce phase separation in a micellar solution of primary amine citrate were described. The critical micelle concentration of 1-octylamine citrate in aqueous solution of tetrabutylammonium bromide was firstly determined.