A convergent "5 + 1" and "5 + 3" synthetic strategy allowed the synthesis of the first examples of bis-betaines 2 and 3, a prototype of phanes that incorporate heterocyclic betaines. The structure of the quadrupolar macrocyclic systems 2 and 3 together with the dicationic [1(6)]- and [1(8)] meta-heterophane precursors 5*2X and 6*2X were examined by spectroscopy using 1H and 13C NMR techniques together with 1H-DNMR studies and electrospray ionization mass spectrometry.