The intrinsic physical properties of nanostructures of metals and their oxides are altered when they are prone to surface oxidation in ambient atmosphere. To overcome this limitation, novel synthesis methodologies are required. In this study, solid octahedral shapes of MnO limit the inward oxygen diffusion compared to that of the MnO-nanoparticle-assembled octahedra. In addition to morphology control, which restricts the thickness of the Mn3O4 surface layer, the binding chemistry of the surfactants plays an essential role. For example, the Mn3O4 surface layer is 0.4 nm thinner with trioctylphosphine oxide than with trioctylamine as the surfactant. The nanostructures were prepared by varying the surfactants, surfactant-to-precursor molar ratio, accelerating agent, and reaction heating rate. The surface oxidation of MnO nano-octahedra was probed by Rietveld analysis of X-ray diffraction patterns and X-ray photoelectron spectroscopy and characterized by magnetic measurements, as the presence of ferrimagnetic Mn3O4 shell on the antiferromagnetic MnO core provides an exchange coupling at the core-shell interface. Thicker the Mn3O4 shell, higher is the exchange-biased hysteresis loop shift.