The decoration of pâtype nickel oxide (NiO) with nâtype hematite (αâFe2O3) to achieve vertically ordered 1D nanostructures is an attractive strategy to enhance gas sensing properties. Herein, the authors report a facile method for αâFe2O3 decoration of the whole surface of vertical NiO nanorods. An NiO/Fe heterostructure is deposited in multiple steps using a glancing angle deposition method, which is followed by the oxidation of Fe into αâFe2O3. Thermally agglomerated αâFe2O3 nanoparticles are uniformly distributed on the whole surface of the NiO nanorods. Due to the αâFe2O3 decoration, the NiO nanorods exhibit a coralâlike rough surface and, more interestingly, their preferential crystallographic orientation changed from (111) to (200). Compared to bare NiO nanorods, the αâFe2O3âdecorated NiO nanocorals exhibit a 45.4 times higher response to 50 ppm toluene (C7H8) at 350 °C. Their theoretical detection limit for C7H8 is calculated to be â22 ppb. The observed unprecedented synergetic effects of αâFe2O3âdecorated NiO nanocorals for the extremely selective C7H8 sensing, as well as their facile synthetic route, establish a new perspective on heterostructured metal oxide 1D nanostructures for selective gas sensing.