Although ion exchange is often depicted as a process driven by electrostatic forces, ionic solvation or hydrophobic forces contribute greatly to ion exchange selectivity and is often the dominant factor. On a variety of commercial anion exchange columns, monovalent ClO4- elutes after doubly charged SO42- and even triply charged PO43-. For identically charged alkali metal ions, electrostatic charge densities based on crystal radii would suggest Li+ to be the most strongly retained on a cation exchanger. In practice, it is typically the least strongly held cation on most cation exchangers, because of its very high hydration energy and with most eluents its capacity factor approaches zero. Even when the ion is very poorly solvated, as with tetraalkylammonium (NR4+) cations, there has never been a report on a polymeric ion exchanger of an ideal electrostatic selectivity order where NR4+ cations elute in their increasing charge density order: R = n-butyl first, followed by n-propyl, ethyl, and last, methyl. We show that this selectivity order is easily achieved on recently described methracrylate-based monolithic capillary cation exchange columns (Ueki, Y.; Umemura, T.; Li, J. X.; Odake, T; Tsunoda, K. Anal. Chem. 2004, 76, 7007-7012) with minor amounts of hydroorganic modifiers. Indeed, under such conditions, Li+ (and other alkali cations) elutes after NMe4+.