This paper presents a new approach based on phased array ultrasonic technique (PAUT) with full matrix capture (FMC) to effectively measure acoustic properties such as ultrasonic wave velocity and attenuation coefficient and to evaluate material degradation. This paper also proposes the use of PAUT with FMC, to simultaneously generate and detect ultrasonic waves such as longitudinal, shear, and Rayleigh waves in the material. A theoretical model is developed to derive the analytical solution of ultrasonic waves induced in the material by an ultrasonic phased array probe. Based on the theoretical prediction, experiments are carried out on AISI 316L stainless steel specimen of 3 mm thickness, and a 2D finite element model is built to verify the generation and detection of these waves. Furthermore, measurements of acoustic properties are carried out on the specimen using the proposed approach as well as the conventional ultrasonic testing (CUT) technique and their sensitivities are compared. The measurements of time-of-flight and back-wall echo amplitude are more accurate with the proposed approach than the CUT technique, which makes the former technique better than the latter for the evaluation of material degradation. Finally, experiments are performed on AISI 316L specimen degraded with different levels of tensile stress to verify the capability of PAUT with FMC. The results show that the velocities and attenuation coefficient increase with an increase in tensile stress until material fracture. This phenomenon is interpreted as resulting from microstructural changes such as dislocations during material degradation. From the experimental results, it is proposed that PAUT with FMC can potentially be used to evaluate early-stage materials degradation.