The purpose of this study is to use acoustic emission (AE) technology to explore the changes in the interface and mechanical properties of GF/VER composite materials after being treated with NaOH and to analyze the optimal modification conditions and damage propagation process. The results showed that the GF surface became rougher, and the number of reactive groups increased after treating the GF with a NaOH solution. This treatment enhanced the interfacial adhesion between the GF and VER, which increased the interfacial shear strength by 25.31% for monofilament draw specimens and 27.48% for fiber bundle draw specimens compared to those before the GF was modified. When the modification conditions were a NaOH solution concentration of 2 mol/L and a treatment time of 48 h, the flexural strength of the GF/VER composites reached a peak value of 346.72 MPa, which was enhanced by 20.96% compared with before the GF was modified. The process of damage fracture can be classified into six types: matrix cracking, interface debonding, fiber pullout, fiber relaxation, matrix delamination, and fiber breakage, and the frequency ranges of these failure mechanisms are 0~100 kHz, 100~250 kHz, 250~380 kHz, 380~450 kHz, 450~600 kHz, and 600 kHz and above, respectively. This paper elucidates the fracture process of GF/VER composites in three-point bending. It establishes the relationship between the AE signal and the interfacial and force properties of GF/VER composites, realizing the classification of the damage process and characterizing the mechanism. The frequency ranges of damage types and failure mechanisms found in this study offer important guidance for the design and improvement of composite materials. These results are of great significance for enhancing the interfacial properties of composites, assessing the damage and fracture behaviors, and implementing health monitoring.