In this work, a series of Mn-Co rod-like layered catalysts self-assembled from porous rod aggregates were fabricated by a simple solvothermal approach. Compared with Mn-Co particles, Mn-Co rods exhibited a much better SCR performance (achieving >93% NOx conversion at 75 degrees C) and high N-2 selectivity. The outstanding catalytic performance was mainly attributed to the large specific surface area and unique rod-like mesoporous structures, which could provide more active sites and reaction centers for the reaction gas to further promote the de-NOx performance of the catalyst. In addition, the high atomic ratio of Mn4+/Mn on the catalyst surface, strong acid strength, and large acidity amount also had positive effects on its catalytic activity. Moreover, Mn-Co rods possessed a better catalytic cycle performance and more surface acid sites due to the synergistic effect between Co and Mn species.