During the process of sodium storage in hard carbon anodes, the significance of surface oxygen functional groups cannot be overlooked. In this work, we utilize starch as raw material to synthesize hard carbon by the process of pre-oxidation and two-step carbonization. XPS analysis reveals that pre-oxidation bolsters the presence of CO bonds, thereby providing more active sites. TEM analysis reveals that hard carbon with pseudo-graphite and graphite-like structure is obtained at relatively high carbonization temperature (1400 °C), and the formation of closed pores results in lower specific surface area. The introduction of appropriate oxygen-containing groups in pre-oxidation process can facilitate the cross-linking of starch chains, promoting the increase of defect sites and the sodium storage performance of hard carbon. A series of samples are prepared at various pre-oxidation temperature. Among them, P200-HC obtained after pre-oxidation at 200 °C and carbonization at 1400 °C exhibits the highest reversible specific capacity of 342.7 mAh g−1 at current density of 0.1 C with an initial Coulombic efficiency of 71.1 %, and capacity retention of 87.3 % at current density of 1 C. The work presents a viable approach for the synthesis of hard carbon derived from starch, thereby expanding the design tactic of sodium-ion batteries with improved performance.