A series of potassium-promoted spinels (Mn, Fe, Co) were prepared with various K⁺ promoter locations: on the surface (surface promotion) or in the bulk (formation of new layered and tunneled nanostructures via solid state reaction). All prepared samples were characterized by means of X-ray diffraction, Raman spectroscopy, X-ray fluorescence and N₂-BET specific surface area analysis. Catalytic activity in soot combustion in different reaction conditions was investigated (tight contact, loose contact, loose contact with NO addition). It was shown that in all cases the nanostructuration is more effective than the surface promotion, with the layered structures of KCo₄O₈, KMn₄O₈ being the most catalytically active phases, lowering the soot combustion down to 250 °C. The difference in activity between tight and loose contacts can be bridged in the presence of NO due to its transformation into NO₂, which acts as the oxygen carrier from the catalyst surface into soot particles, eliminating the soot-catalyst contact difference.