Based on the rough surface topography with fractal parameters and the Monte–Carlo simulation method for secondary electron emission properties, we analyze the secondary electron yield (SEY) of a metal with rough surface topography. The results show that when the characteristic length scale of the surface, G, is larger than 1 × 10−7, the surface roughness increases with the increasing fractal dimension D. When the surface roughness becomes larger, it is difficult for entered electrons to escape surface. As a result, more electrons are collected and then SEY decreases. When G is less than 1 × 10−7, the effect of the surface topography can be ignored, and the SEY almost has no change as the dimension D increases. Then, the multipactor thresholds of a C-band rectangular impedance transfer and an ultrahigh-frequency-band coaxial impedance transfer are predicted by the relationship between the SEY and the fractal parameters. It is verified that for practical microwave devices, the larger the parameter G is, the higher the multipactor threshold is. Also, the larger the value of D, the higher the multipactor threshold.