Salvia officinalis (commonly called Sage) and similar plants contain many compounds of pharmaceutical interest and are used as a tea or in various pharmaceutical products. In this work, the use of CE for analysis of aqueous or ethanolic extracts from various Salvia plants has been studied. Especially, several buffers like borate, phosphate, acetate, etc., were examined under different concentrations, pH, separation voltage, injection time, and other parameters to find the optimal separation conditions. The optimization was also performed using experimental design and artificial neural networks. The optimal conditions were: separation voltage +20 kV, 40 mM buffer borate, pH 9.2, injection time 5 s, and UV detection at 280 nm. A new CE method has been developed, validated, and applied to analyze samples of S. officinalis from various countries.