In the field of non-destructive testing (NDT) for concrete structures, the traditional air-coupled impact-echo technology often has the problems of complex operation and low efficiency. In order to solve these problems, this study uses Comsol software to establish a finite element model (FEM) of the concrete structure with different void sizes and obtains the variation rule of peak frequency. The recognition property of the concrete void based on peak frequency is proposed, which is explained and validated by relevant theory and experiments. The results show that compared with the depth of the void, the influence of the void width on the peak frequency increases significantly. When the void width is greater than 0.3 m, the peak frequency of the sound wave decreases with the increase in the width, and the change is obvious. This paper describes the applicability of concrete void depth less than 0.4 m for the air-coupled method and, when the concrete void depth is less than 0.4 m, the peak frequency can be used to effectively identify void widths greater than 0.3 m. The research results will be beneficial to void detection of concrete structures such as tunnel lining and pavements.