This paper introduces topological Slepians, i.e., a novel class of signals defined over topological spaces (e.g., simplicial complexes) that are maximally concentrated on the topological domain (e.g., over a set of nodes, edges, triangles, etc.) and perfectly localized on the dual domain (e.g., a set of frequencies). These signals are obtained as the principal eigenvectors of a matrix built from proper localization operators acting over topology and frequency domains. Then, we suggest a principled procedure to build dictionaries of topological Slepians, which theoretically provide non-degenerate frames. Finally, we evaluate the effectiveness of the proposed topological Slepian dictionary in two applications, i.e., sparse signal representation and denoising of edge flows.