Symmetric Positive Definite (SPD) matrices in the form of region covariances are considered rich descriptors for images and videos. Recent studies suggest that exploiting the Riemannian geometry of the SPD manifolds could lead to improved performances for vision applications. For tasks involving processing large-scale and dynamic data in computer vision, the underlying model is required to progressively and efficiently adapt itself to the new and unseen observations. Motivated by these requirements, this paper studies the problem of online dictionary learning on the SPD manifolds. We make use of the Stein divergence to recast the problem of online dictionary learning on the manifolds to a problem in Reproducing Kernel Hilbert Spaces, for which, we develop efficient algorithms by taking into account the geometric structure of the SPD manifolds. To our best knowledge, our work is the first study that provides a solution for online dictionary learning on the SPD manifolds. Empirical results on both large-scale image classification task and dynamic video processing tasks validate the superior performance of our approach as compared to several state-of-the-art algorithms.