We study the relation between two special classes of Riemannian Lie groups with a left-invariant metric : The Einstein Lie groups, defined by the condition , and the geodesic orbit Lie groups, defined by the property that any geodesic is the integral curve of a Killing vector field. The main results imply that extensive classes of compact simple Einstein Lie groups are not geodesic orbit manifolds, thus providing large-scale answers to a relevant question of Y. Nikonorov. Our approach involves studying and characterizing the -invariant geodesic orbit metrics on Lie groups for a wide class of subgroups that we call (weakly) regular. By-products of our work are structural and characterization results that are of independent interest for the classification problem of geodesic orbit manifolds.

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