The stepped surfaces in nanoscale zero-valent iron (nZVI) play an essential role for environmental application. However, there is still currently a deficiency in the atomic understanding of stepped surface properties due to the limitation of the computational methodology. In this study, stepped Fe(210) and (211) surfaces were theoretically investigated using density functional theory (DFT) computations in terms of the flat Fe(110) surface. Our results suggest that the consideration of van der Waals (vdW) interaction correction is beneficial for the DFT study on Fe-based systems. The DF-cx method is found to be the most promising vdW correction method. The DF-cx results reveal that the stepped Fe(210) and Fe(211) surfaces experience significant surface relaxation and abnormal trends in their work function. Their electronic properties and reactivities of the surface atoms are strongly affected by the Fe coordination numbers and the strong adsorption strengths of oxygen on the surfaces are dependent on both the coordination number of the adsorbed atoms and the geometry of the adsorption sites.