A directed assembly process to form C-4-symmetric, vanadate-centered quadruplexes, for the first time, from a given chiral oxidovanadium(V) complex allows for highly efficient K+- and Ag (+)-specific transport from aqueous phase containing three other alkali metal cations into organic solvents, reminiscent of the K+ specific transport exerted by four homochiral glycine residues of the opening site in KcsA membrane protein.