Nowadays, the anti-reflective (AR) structures are essential in many applications like display screens, photovoltaic structures and light detection and ranging. Traditionally, the AR surfaces are almost multilayer (ML) structures to minimize the reflection value by producing the destructive interference of reflected light beams at the layers’ interfaces. In the new and advanced AR surfaces, nanostructures (NS) are proposed and used for minimizing the reflection. In this paper, we propose a temperature switchable AR-ML-NS, based on vanadium dioxide (VO2) phase transition from semiconductor to metallic state around the critical temperature of 68 °C. Here, a pyramidal NS ofVO2 is considered on top surface of aML which minimizes the light reflection of the structure. While some AR structures may work in some restricted light wavelengths, here our proposed structure’s AR wavelength region can be tuned between the visible and near-infrared (NIR) region through the thermal phase transition ofVO2. VO2 phase control leads to a temperature-switchable AR structure, which is of great importance for investigating different switchable AR structures.