Fracture characterization is essential for estimating the stimulated reservoir volume and guiding subsequent hydraulic fracturing stimulations in shale reservoirs. Laboratory fracturing experiments can help provide theoretical and technical guidance for field operations. In this study, hydraulic fracturing experiments on the shale samples from Niutitang Formation in Hunan Province (China) under a uniaxial loading condition are conducted. The multifractal method is used to analyze the acoustic emission (AE) signals and characterize fracture initiation and propagation. The hydraulic fracturing process can be divided into three stages based on the characteristics of AE signals: the initial stage, the quite stage, and the fracturing stage. The multifractal analysis results showed that: (1) the value of the spectrum width, Δα, continues to increase as the energy accumulates until the fracturing stage starts; and (2) the difference in the multifractal spectrum values, Δf, reflects the relationship between small and large signal frequencies and can quantify the fracture scale, i.e., the lower the Δf, the larger the fracture scale and vice versa. The results were further verified using a time-frequency analysis of the AE signals and micro-CT scanning of the samples. This study demonstrates that the multifractal method is feasible for quantitatively characterizing hydraulic fractures and can aid field hydraulic fracturing operations.