Thermochromic or electrochromic materials may be exploited to develop a multilayer structure which can reversibly change their optical properties (e.g., emittance and reflectance) with either the surrounding temperature or an applied voltage, respectively. Accordingly, electrochromic materials feature an active thermal control system requiring an ongoing manipulation of voltage inputs as stimulant while the thermochromic materials feature a passive thermal control system which is often preferred for space applications. The present study aims to design and develop a smart multilayer structure armed with thermochromic material to offer a positive emittance switching at a certain phase-transition temperature as close as to the room temperature. The materials, thickness, and sequence for each layer is determined such that the structure can provide a wide dynamic range of emissivity with temperature in the mid-infrared wavelength region to ensure the effectiveness of the proposed passive thermal control system for the space vehicles. The thermochromic layer considered for the present study is Vanadium Dioxide whose phasetransition temperature is 68 °C. To achieve an emittance switching temperature close to the room temperature, this study also strives to reduce phase-transition temperature of thermochromic system using doping process. The proposed multilayer structure is grown using thin film deposition techniques consisting mainly of Magnetron sputtering and electron-beam evaporation with optimal operating conditions. After fabricating the proposed structure, an experimental apparatus is designed and developed which enables direct measurement of the emitted power from the coating under different operating conditions. Using the proposed test setup based on calorimetric approach, the total hemispherical emittance can directly be explored.