The migration behavior of Se(IV) and Re(VII) in muscovite was studied by capillary diffusion method and diffusion cell method. The results show that diffusion accelerates when the density decreases and the ionic strength increases. At the same time, pH also significantly affects their migration. The apparent diffusion coefficient ranges from 10–11 to 10–9 m/s2. This work can provide potential applications in deep geological nuclear waste repositories.