The role of ionic electrostatics in colloidal processes is well-understood in natural and applied contexts; however, the electrostatic contribution of zwitterions, known to be present in copious amounts in extremophiles, has not been extensively explored. In response, we studied the effects of glycine as a surrogate zwitterion, ion, and osmolyte on the electrostatic forces between negatively charged mica–mica and silica–silica interfaces. Our results reveal that while zwitterions layer at electrified interfaces and contribute to solutions’ osmolality, they do not affect at all the surface potentials, the electrostatic surface forces (magnitude and range), and solutions’ ionic conductivity across 0.3–30 mM glycine concentration. We infer that the zwitterionic structure imposes an inseparability among positive and negative charges and that this inseparability prevents the buildup of a counter-charge at interfaces. These elemental experimental results pinpoint how zwitterions enable extremophiles to cope with the osmotic stress without affecting finely tuned electrostatic force balance.