Normally, polarimetric SAR classification is a high-dimensional nonlinear mapping problem. In the realm of pattern recognition, sparse representation is a very efficacious and powerful approach. As classical descriptors of polarimetric SAR, covariance and coherency matrices are Hermitian semidefinite and form a Riemannian manifold. Conventional Euclidean metrics are not suitable for a Riemannian manifold, and hence, normal sparse representation classification cannot be applied to polarimetric SAR directly. This paper proposes a new land cover classification approach for polarimetric SAR. There are two principal novelties in this paper. First, a Stein kernel on a Riemannian manifold instead of Euclidean metrics, combined with sparse representation, is employed for polarimetric SAR land cover classification. This approach is named Stein-sparse representation-based classification (SRC). Second, using simultaneous sparse representation and reasonable assumptions of the correlation of representation among different frequency bands, Stein-SRC is generalized to simultaneous Stein-SRC for multi-frequency polarimetric SAR classification. These classifiers are assessed using polarimetric SAR images from the Airborne Synthetic Aperture Radar (AIRSAR) sensor of the Jet Propulsion Laboratory (JPL) and the Electromagnetics Institute Synthetic Aperture Radar (EMISAR) sensor of the Technical University of Denmark (DTU). Experiments on single-band and multi-band data both show that these approaches acquire more accurate classification results in comparison to many conventional and advanced classifiers.