Porous micro-/nanostructures are of great interest in many current and emerging areas of technology. In this paper, porous microspheres composed of LaFeO3 nanoparticles were prepared by a convenient and effective method. The obtained microspheres have been structurally characterized by X-ray diffraction analysis (XRD), which confirms the single crystalline orthorhombic structure. By using scanning electron microscopy (SEM), it can be seen that porous LaFeO3 microspheres with rough surface were assembled from a large amount of interconnected nanoparticles. And transmission electron microscopy (TEM) image has also confirmed their porous feature. A subsequent plausible formation mechanism of porous LaFeO3 microspheres has been explained in accordance with the Ostwald ripening process. Moreover, gas sensing investigation showed that the sensor based on porous LaFeO3 microspheres exhibited potential applications in monitoring acetone gas due to their unique morphology and porous structure. (C) 2015 Elsevier B.V. All rights reserved.