Nanosized α-Fe2O3 (ca. 50nm) and Li–Fe composite oxides (ca. 29nm) powders were synthesized via gel polymer route. The gels were obtained with thermal polymerization of acrylic acid solutions of iron and lithium nitrates. The calcination of these gels at temperatures from 300°C to 500°C results in α-Fe2O3 from Fe(NO3)3 precursor and Li–Fe composite oxides Li2O–Fe3O4–LiFeO2 from a mixed precursors of Fe(NO3)3 and LiNO3. Thermal gravimetric analysis, X-ray diffraction and transmission electron microscopy were used to investigate the precursors and products. The electrochemical performance of the Fe-based oxides was also evaluated. After 200 cycles, their capacity can be as high as 1300mAh/g for α-Fe2O3 and 1400mAh/g for Li–Fe oxide while the initial capacity loss is as low as 21.8%. The Li–Fe oxide electrodes exhibit better capacity retention than the α-Fe2O3 electrodes. They are interesting negative electrodes for high energy density lithium-ion batteries.