We obtain local parametrizations of classical non-compact Lie groups where adjoint invariants under maximal compact subgroups are manifest. Extension to non-compact subgroups is straightforward. As a by-product parametrizations of the same type are obtained for compact groups. They are of physical interest in any theory gauge invariant under the adjoint action, typical examples being the two dimensional gauged Wess-Zumino-Witten-Novikov models where these coordinatizations become of extreme usefulness to get the background fields representing the vacuum expectation values of the massless modes of the associated (super) string theory.