On the basis of non-linear effect studies, new diagnostic and defectoscopic methods have been designed which are based on the elastic wave non-linear spectroscopy. The non-linear ultrasonic spectroscopy brings new prospects into the acoustic non-destructive testing of material degradation. Poor material homogeneity and, in some cases, the shape complexity of some units used in the building industry, are heavily restricting the applicability of "classical" ultrasonic methods. These linear acoustic methods focus on the energy of waves, which are reflected by structural defects, variations of the wave propagation velocity, or changes in the wave amplitude. However, none of these "linear" wave characteristics is as sensitive to the structure defects as the specimen non-linear response. In this way, non-linear methods thus open new horizons in non-destructive ultrasonic testing, providing undreamed-of sensitivities, application speeds, and easy interpretation. One of the fields in which a wide application range of non-linear acoustic spectroscopy methods can be expected is civil engineering. It is predicted that these advanced techniques can contribute a great deal to the improvement and refinement of the defectoscopic and testing methods in the building industry. The present paper deals with analyzing one of the non-linear ultrasonic defectoscopic methods from the viewpoint of its application to the concrete specimen structural integrity evaluation. Both intact specimens and specimens subject to various kinds of stress have been tested. The effect of structural defects on the elastic wave propagation has been studied.