Porosity in the sol-gel prepared vanadium pentoxide film is created by using templating methods. The morphology, optical and electrochromic properties of the macro- and mesoporous films, prepared in the presence of structure-directing agents such as polystyrene microspheres and triblock copolymer, have been compared with those of dense films. By using various methods to remove the template material, it was shown that the morphology of the vanadium pentoxide film can be controlled and new nanostructures can be created. The transformation of the lamellar into a nanorod structure, observed when the film is heated at 375-500 degrees C for several hours, resulted in the development of an elegant method for the synthesis of vanadium oxide nanostructures. The electrochromic performance of the nanorods prepared through the thermal treatment was found to be superior to that of the vanadium pentoxide with the layered structure, especially in the near-infrared region, demonstrating their potential for electrochromic applications. (C) 2015 The Electrochemical Society. All rights reserved.