We are concerned with the global existence and decay rates of large solutions for the Poisson–Nernst–Planck equations. Based on careful observation of algebraic structure of the equations and using the weighted Chemin–Lerner‐type norm, we obtain the global existence and optimal decay rates of large solutions without requiring the summation of initial densities of a negatively and positively charged species that is small enough. Moreover, the large solution is obtained for initial densities belonging to the low regularity Besov spaces with different regularity and integral indices, which indicates more specific coupling relations between the difference and the summation of negatively and positively charged densities.