Abstract. This paper concerns the approximation of probability measures on R d with respect to the Kullback-Leibler divergence. Given an admissible target measure, we show the existence of the best approximation, with respect to this divergence, from certain sets of Gaussian measures and Gaussian mixtures. The asymptotic behavior of such best approximations is then studied in the small parameter limit where the measure concentrates; this asympotic behavior is characterized using Γ-convergence. The theory developed is then applied to understand the frequentist consistency of Bayesian inverse problems in finite dimensions. For a fixed realization of additive observational noise, we show the asymptotic normality of the posterior measure in the small noise limit. Taking into account the randomness of the noise, we prove a Bernstein-Von Mises type result for the posterior measure. 1. Introduction. In this paper, we study the "best" approximation of a general finite dimensional probability measure, which could be non-Gaussian, from a set of simple probability measures, such as a single Gaussian measure or a Gaussian mixture family. We define "best" to mean the measure within the simple class which minimizes the Kullback-Leibler divergence between itself and the target measure. This type of approximation is central to many ideas, especially including the so-called variational inference [30], that are widely used in machine learning [3]. Yet such approximation has not been the subject of any substantial systematic underpinning theory. The purpose of this paper is to develop such a theory in the concrete finite dimensional setting in two ways: (i) by establishing the existence of best approximations and (ii) by studying their asymptotic properties in a measure concentration limit of interest. The abstract theory is then applied to study frequentist consistency [28] of Bayesian inverse problems.