The isoreticular expansion and functionalization of charged-polarized porosity has been systematically explored by the rational design of eleven isostructural zwitterionic metal-organic frameworks (ZW-MOFs). This extended series of general structural composition {[M3F(L1)3(L2)1.5]•guests}n was prepared by employing the solvothermal reaction of Co and Ni tetrafluoroborates with a binary ligand system composed of zwitterionic pyridinium derivatives and traditional functionalized ditopic carboxylate auxiliary ligands (HL1•Cl = 1-(4