This paper reports the synthesis, morphology, magnetic properties and gas sensing characteristics of mesoporous urchin-like alpha-Fe2O3 superstructures prepared by one-step thermal decomposition of iron nitrate aqueous solution. The advantages of this fabrication technique include simplicity, convenience, efficiency, capability of scale-up fabrication, and good control of product structure and morphology. The urchin-like alpha-Fe2O3 superstructures are made of oriented aggregations of nanorods (diameter similar to 10-130 nm; length similar to 150-700 nm) with an overall size in the range of 0.5-5 mu m. The nanobuilding blocks of the urchin-like superstructures are either single-crystal nanorods or a mixture of single-crystal knotted or branched sub-nanorods and elongated particles. Unusually high intrinsic coercivity, H-i(c), of up to 5.3 kOe and reduced Morin transition temperatures were observed for the urchin-like alpha-Fe2O3 superstructures. The urchin-like alpha-Fe2O3 samples showed excellent gas sensing performance for acetone, ammonia, and ethanol.