Display omitted •Special synthetic routes for Dual-Porosity Mn2O3 Cubes.•Mn2O3 Cubes contain both macropores and mesopores.•Dual-porosity Mn2O3 Cubes show great adsorption capacity for Congo Red. Dual-porosity materials containing both macropores and mesopores are highly desired in many fields. In this work, we prepared dual-porosity Mn2O3 cube materials with large-pore mesopores, in which, macropores are made by using carbon spheres as the hard templates, while the mesopores are produced via a template-free route. The attained dual-porosity Mn2O3 materials have 24nm of large-pore mesopores and 700nm of macropores. Besides, the achieved materials own cubic morphologies with particle sizes as large as 6.0μm, making them separable in the solution by a facile natural sedimentation. Dye adsorption measurements reveal that the dual-porosity materials possess a very high maximum adsorption capacity of 125.6mg/g, much larger than many reported materials. Particularly, the adsorbents can be recycled and the dye removal efficiency can be well maintained at 98% after four cycles. Adsorption isotherm and kinetics show that the Langmuir model and the pseudo-second-order kinetics model can well describe the adsorption process of Congo Red on the dual-porosity Mn2O3 cube materials. In brief, the reported dual-porosity Mn2O3 demonstrates a good example for controlled preparation of dual-porosity materials with large-pore mesopores, and the macropore-mesopore dual-porosity distribution is good for mass transfer in dye adsorption application.