The present work reports the formation of 3D nanoflower-like morphology of iron alkoxide via the anodization of Fe sheet in ethylene glycol (EG) electrolyte. XRD, FESEM, EDX, XPS, Raman and FTIR are applied to characterize the samples. SEM results show that the as-anodized sample is composed of 3D nanoflowers with hierarchical nanosheets beneath it. The average width of the nanoflower petal is ∼25 nm and the length is about 1 μm. The 3D nanoflowers are transformed into spherical nanoparticles (NPs) with uniform size when calcined at elevated temperature. XRD and Raman results indicate that the 3D nanoflowers consist of akaganeite, which transforms into magnetite and hematite by annealing. XPS and FTIR results confirm that the nanoflowers contain significant amounts of F, C and OH, which are drastically decreased after annealing. The formation of 3D nanoflower-like morphology can be attributed to EG. A possible formation mechanism of 3D nanoflowers and their transformation into NPs is proposed. We showed that the morphology of the as-anodized iron oxide can be tailored simply by changing the electrolyte. The anodization of Fe sheet in glycerol-based electrolyte under identical conditions produced nanotubes.