Top-coal structure detection is an important basis for realizing effective mining in fully mechanized cave faces. However, the top-coal structure is very complex and often contains multi-layer gangues, which seriously influence the level of effective mining. For these reasons, this paper proposes a novel multi-frequency ground-penetrating radar (GPR) data-fusing method through a joint sliding window and wavelet transform weighting method to accurately detect the top-coal structure. It possesses the advantages of both high resolution and great detection depth, and it can also integrate multi-frequency GPR data into one composite profile to interpret the internal structure information of top coal in detail. The detection procedure is implemented following several steps: First of all, the multi-frequency GPR data are preprocessed and aligned through a band-pass filter and a zero offset elimination method to establish their spatial correspondences. Secondly, the proposed method is used to determine the time-varying weight values of each frequency GPR signal according to the wavelet energy proportion within the sliding window; also, the edge detection algorithm is introduced to improve the fusion efficiency of the wavelet transform so as to realize the effective fusion of the multi-frequency GPR data. Thirdly, a reflection intensity model of multi-frequency GPR signals traveling in the top-coal is established by using the stratified identification method, and then, the detailed top-coal structure can be inversely interpreted. Finally, the quantitative evaluation criteria, information entropy (IE), space–frequency (SF) and Laplacian gradient (LG), are used to evaluate the multi-frequency GPR data fusion’s effectiveness in laboratory and field environments. The experimental results show that, compared with the genetic, time-varying and wavelet transform fusion method, the fusion performance of the presented method possesses higher values in the IE, SF and LG evaluation criteria, and it also has both the merits of high resolution and great detection depth.