Acicular goethite（a-Fe OOH） and worm-like maghamite（γ-Fe₂O₃） nanostructures have been prepared adopting a novel route, using Na2[Fe（HL）2（H2O）2] chelate complex in alkaline medium. It is found that concentration of hydrated Fe（III） ions increased with increasing temperature, which later play a key role in generation of different phases of iron oxide. Phase and morphology of the products are investigated using XRD, FTIR, SEM, and TEM analysis. Using UV–Vis spectra, various electronic transitions of goethite and maghamite particles are examined. Maghamite nanostructures exhibit superparamagnetic property at room temperature. On the basis of experimental observations and analytical data, growth mechanism of the nanostructures is discussed.