Vibrations caused by downhole operations often induce coal and gas outburst accidents in tectonic zone coal seams. To clarify how vibration affects the pore structure, gas desorption, and diffusion capacity of tectonic coal, isothermal adsorption-desorption experiments under different vibration frequencies were carried out. In this study, high-pressure mercury intrusion experiments and low-pressure liquid nitrogen adsorption experiments were conducted to determine the pore structures of tectonic coal before and after vibration. The pore distribution of vibration-affected tectonic coal, including local concentration, heterogeneity, and connectivity, was analyzed using multifractal theory. Further, a correlation analysis was performed between the desorption diffusion characteristic parameters and the pore fractal characteristic parameters to derive the intrinsic relationship between the pore fractal evolution characteristics and the desorption diffusion characteristics. The results showed that the vibration increased the pore volume of the tectonic coal, and the pore volume increased as the vibration frequency increased in the 50 Hz range. The pore structure of the vibration-affected tectonic coal showed multifractal characteristics, and the multifractal parameters affected the gas desorption and diffusion capacity by reflecting the density, uniformity, and connectivity of the pore distribution in the coal. The increases in the desorption amount (Q), initial desorption velocity (V0), initial diffusion coefficient (D0), and initial effective diffusion coefficient (De) of the tectonic coal due to vibration indicated that the gas desorption and diffusion capacity of the tectonic coal were improved at the initial desorption stage. Q, V0, D0, and De had significant positive correlations with pore volume and the Hurst index, and V0, D0, and De had negative correlations with the Hausdorff dimension. To a certain extent, vibration reduced the local density regarding the pore distribution in the coal. As a result, the pore size distribution was more uniform, and the pore connectivity was improved, thereby enhancing the gas desorption and diffusion capacity of the coal.