Pulsed spray evaporation chemical vapour deposition (PSE-CVD), an elaborate CVD process, was employed to synthesize thin films of α-Fe2O3 for the catalytic combustion of propene. According to X-ray diffraction and Raman spectroscopy, the alpha structure type was presented as the unique phase. α-Fe2O3 with fine crystalline structure was revealed by Scanning electron microscopy, and probed in depth for the first time by Helium ion microscopy. Energy dispersive X-ray microscopy and X-ray photoelectron spectroscopy displayed an overview of the chemical composition of the samples. In-situ emission FTIR spectroscopy was used for the accurate determination of the thermal stability of the samples at around 500 °C, and temperature-programmed reduction was performed to correlate the catalytic performance and reduction properties of the obtained α-Fe2O3 thin films. The results showed that the increase of the deposition temperature leads to significant changes of film morphology, chemical composition and reduction properties, with a direct consequence on the catalytic performance. α-Fe2O3 prepared at low temperature (350 °C) exhibited high activity towards the deep oxidation of propene, which was attributed to its good reducibility and the plate-like structures. The alternate reduction and oxidation of the oxide surface (favored by the bulk oxygen migration towards the surface) and replenishment of bulk oxygen by gas-phase oxygen, suggests that the oxidation of propene may proceed according to the Mars van Krevelen mechanism. The morphology and surface composition of the prepared samples remain the same before and after the catalytic test, demonstrating very good stability and reproducibility. We thus conclude that α-Fe2O3 effective in propene conversion can be selectively synthesized with PSE-CVD.