Citric acid‐based sol‐gel method has been used to synthesize metal oxides widely. Iron‐based one‐dimensional nanostructured materials, including Fe2O3 nanotubes and Fe3O4 nanofibers, have been successfully prepared by directly annealing electrospun citric acid‐based precursor fibers under different atmospheres in this study. Thermo‐gravimetric and differential thermal analyses were carried out from room temperature to 800°C under air and argon atmosphere, respectively. The results reveal the formation mechanisms for Fe2O3 nanotube and Fe3O4 nanofiber. Fe2O3 tubular structures with average inner diameter about 500 nm and wall thickness about 20 nm were obtained. Fe3O4 nanoparticles were self‐assembled along the one dimensional orientation to form Fe3O4 nanofibers with average diameter around 500 nm. The reflection losses as a function of frequency for the samples with 23 and 33 wt% Fe3O4 nanofibers in paraffin were examined. The frequency dependence of reflection losses under various matching thicknesses (2, 3, 4, 6 and 8 mm) was simulated. The as‐fabricated Fe3O4 nanofibers can be believed to be promising candidates as highly effective microwave absorbers.