This paper investigates the generation of passive intermodulation (PIM) in coaxial connectors during vibration. A series of experiments were designed and the simulation model and method were proposed for understanding these phenomena. We found that PIM is mainly influenced by the contact stress and contact surface roughness during vibration. Thus, a power spectral density method is presented to identify the roughness parameter of contact surface based on the Weierstrass–Mandelbrot model, and the simulation model and method were verified by the relative experiments. Eventually, some suggestions for engineering application were provided.