Rational modification of interfacial structure and chemistry can help effectively tailor the reactivity and stability of heterogeneous catalysts regardless of their elemental or compound natures. Herein, a diluted acidic treatment was designed and utilized to modify the surface structure and chemistry of spinel Co3O4 nanoparticles. Such a chemical leaching strategy has significantly promoted the propane oxidation activity of the PGM-free Co3O4 nanocrystal aggregates, With a much higher activity than the commercial Al2O3 supported Pt and Pd catalysts, these leached nanoparticle aggregates exhibited much more abundant defects, surface Co2+ and chemisorbed oxygen species. Such surface-modified Co3O4 nanocatalysts have displayed excellent and stable propane oxidation efficiency independent of both O-2 and C3H8 concentrations, where the activities of both commercial Pt (or Pd)/Al2O3 and self-made Pt (or Pd)/CeO2 catalysts were greatly affected by different O-2 and C3H8 concentrations. Meanwhile, the Co3O4 nanocrystal aggregates catalyst exhibited good performance in presence of water or sulfur dioxide. This facile chemical leaching based technique provides a potential means to make highly active and stable oxide catalysts.