The formation mechanism of tight oxide scale on the microalloyed steel was investigated at temperatures of 550–850 °C in dry air. Microstructural characterisations reveal that the spallation of oxide scale dominates at the centre of coarse grains on the oxidation initiation. The fine-grained steel improves the adhesive properties of oxide scale by enhanced grain-boundary diffusion. The lower activation energy and higher oxidation rate accelerate cation/anion migration along grain boundaries, leading to high magnetite content in the oxide scale. The approach by grain refinement at initial oxidation has been proposed to generate the pickle-free tight oxide scale.