Abstract: Methods for controlling and varying electroosmotic flow in coated capillary electrophoresis columns under electrophoretic conditions are disclosed. The methods described herein involve varying the concentration of a multi-valent buffer compound in electrophoresis buffer compositions in order to control the electroosmotic flow in capillary columns having interior surfaces coated with charged organic coatings. Increasing the concentration of a multi-valent buffer compound which has a charge opposite the charge of the organic coating, in the electrophoresis buffer results in a decrease in electroosmotic flow. Decreasing the concentration of a multi-valent buffer compound results in an increase in electroosmotic flow. The ability to control electroosmotic flow provides enhanced resolution and optimizes separations of electrophoresis sample components.