Control over the different polymorphs of vanadium oxide that possess electrical switching properties is advancing rapidly as a result of the need to address energy-efficiency issues; an example of which is the intelligent regulation of infrared light demonstrated by these polymorphs. Recent advances in the development of new vanadium oxide structures as well as their promising electrical switching properties are summarized here. Theoretical analysis and experimental results suggest that the presence of infinite vanadium ion chains in the crystal structure plays a decisive role in determining the electrical properties of vanadium oxides. The successful synthesis of new vanadium oxide materials and their nanostructures not only promotes a mechanistic understanding of the temperature-driven electrical switching properties but also provides the right materials for constructing smart devices that can selectively filter out infrared light.