Catalytic performance is largely dependent on how the structures/compositions of materials are designed. Herein, CeO2-MnOx binary oxide catalysts with a hierarchical/porous structure are prepared by a facile and efficient method, which involves the preparation of the hierarchical Ce-Mn coordination polymer (CPs) precursor, followed by a thermal treatment step. The obtained CeO2-MnOx catalysts not only well inherit the hierarchical structure of Ce-Mn CPs, but also possess porous and hollow features due to the removal of organic ligands and heterogeneous contraction during the calcination process. In addition, the effect of the Mn/Ce ratio is also studied to optimize catalytic performance. Specifically, the as-prepared CeO2-MnOx (5 : 5) catalyst exhibits excellent catalytic performance toward CO oxidation and selective catalytic reduction (SCR) of NO with NH3 at low temperatures. Based on the characterization results, we propose that the special hierarchical structure, high surface area, strong synergistic interaction between CeO2 and MnOx, and high content of active Ce3+, Mn4+ and Osurf are collectively responsible for its remarkable catalytic performance.