Waste heat dissipated in the exhaust system in a combustion engine represents a major source of energy to be recovered and converted into useful work. A waste heat recovery system (WHRS) based on an Organic Rankine Cycle (ORC) is a promising approach, and it gained interest in the last few years in an automotive industry interested in reducing fuel consumption and exhaust emissions. Understanding the thermodynamic response of the boiler employed in an ORC plays an important role in steam cycle performance prediction and control system design. The aim of this study is, therefore, to present a methodology to study these devices by means of pattern recognition with infrared thermography. In addition, the experimental test bench and its operating conditions are described. The methodology proposed identifies the wall coordinates, traces the paths, and tracks the wall temperature along them in a way that can be exported for subsequent post-processing and analysis. As for the results, through the wall temperature paths on both sides (exhaust gas and working fluid), it was possible to quantitatively estimate the temperature evolution along the boiler and, in particular, the beginning and end of evaporation.