Pressure vessels are widely used in industrial fields, and some of them are safety-critical components in the system—for example, those which contain flammable or explosive material. Therefore, the pressure of these vessels becomes one of the critical measurements for operational management. In the paper, we introduce a new approach to the design of non-intrusive pressure sensors, based on ultrasonic waves. The model of this sensor is built based upon the travel-time change of the critically refracted longitudinal wave (LCR wave) and the reflected longitudinal waves with the pressure. To evaluate the model, experiments are carried out to compare the proposed model with other existing models. The results show that the proposed model can improve the accuracy compared to models based on a single wave.