Concrete cover has an important role in reinforced concrete (RC) structures because it protects reinforcement bars from the bad effects of weather, fire, and bad environmental conditions that cause the corrosion of the reinforcements. Although it is an essential parameter to be considered for structural health monitoring (SHM), its detection by infrared thermography, especially in the heating phase, has not been accessed yet. The detailed analysis and discussions of physical phenomena, known as diffraction and interference, affecting the thermograms during the detection of the steel bars by microwave thermography have given an essential key for resolving this issue. The present paper proposes an innovative methodology with microwave thermography for determining the concrete cover thickness of one-layer reinforcements (12 mm in diameter and regularly placed at 10 cm) in an RC wall (1 m × 1m × 6.5 cm). By using the transmission approach with five angles of microwave antenna direction (0°, 15°, 30°, 45°, and 60°) and the Snell-Descartes law and linear law, the proposed methodology leads us to deduce the approximate value of the concrete cover thickness (37.74 mm), which is close to the real value (38 mm), as well as the spacing of the steel bars and dielectric constant of the concrete. The detection of the concrete cover thickness is another new remarkable achievement of infrared thermography methods.