In the present paper, a numerical investigation of a jet-ejector is carried out using a real gas model of R1234yf. The prototype under investigation works with specific operating conditions of a jet-ejector refrigeration system intended for waste heat recovery in an internal combustion engine (ICE). In the first instance, the geometry optimization involving nozzle exit diameter, mixing chamber diameter, and nozzle exit position (NXP) is performed. Once the optimum geometry has been obtained, the jet-ejector prototype is tested with different operating pressure ratios to determine its off-design performance. The flow structure in relevant cases has been examined with an emphasis on critical and subcritical modes. The flow phenomena occurring during expansion, entrainment, and mixing processes are discussed so performance degradation can be directly related to physical processes. The analysis has been completed fitting simulated points to critical and subcritical planar surfaces. The results in terms of goodness of fit are satisfactory so the jet-ejector performance in off-design operating conditions can be reflected through simple mathematic models. When the overall cycle is assessed by using previous computational fluid dynamics (CFD) maps, it is observed that the achievable cooling drops significantly when an ambient temperature of 31 °C is exceeded.