In the first part of the paper we investigate some geometric features of Moser-Trudinger inequalities on complete non-compact Riemannian manifolds. By exploring rearrangement arguments, isoperimetric estimates, and gluing local uniform estimates via Gromov's covering lemma, we provide a Coulhon, Saloff-Coste and Varopoulos type characterization concerning the validity of Moser-Trudinger inequalities on complete non-compact n−dimensional Riemannian manifolds (n ≥ 2) with Ricci curvature bounded from below. Some sharp consequences are also presented both for non-negatively and non-positively curved Riemannian manifolds, respectively. In the second part, by combining variational arguments and a Lions type symmetrization-compactness principle, we guarantee the existence of a non-zero isometryinvariant solution for an elliptic problem involving the n−Laplace-Beltrami operator and a critical nonlinearity on n−dimensional homogeneous Hadamard manifolds. Our results complement in several directions those of Y. Yang [J. Funct. Anal., 2012].