Understanding streaming potential generation in porous media is of high interest for hydrological and reservoir studies as it allows to relate water fluxes to measurable electrical potential distributions. This streaming potential generation results from an electrokinetic coupling due to the presence of an electrical double layer developing at the interface between minerals and pore water. Therefore, the pore sizes of the porous medium are expected to play an important role in the streaming potential generation. In this work we use 2‐D pore network simulations to study the effect of the pore size distribution upon this electrokinetic mechanism. Our simulations allow a detailed study of the influence of a large range of permeabilities (from 10−16 to 10−10 m2) for different ionic concentrations (from 10−4 to 1 mol/L). We then use and compare two different approaches that have been used over the last decades to model and interpret the streaming potential generation: the classical coupling coefficient or the effective excess charge density, which has been defined recently. Our results show that the four pore size distributions tested in the present work have a restricted influence on the coupling coefficient for ionic concentration smaller than 10−3 mol/L while it completely drives the behavior of the effective excess charge density over orders of magnitude. Then, we use these simulation results to test an analytical model based on a fractal pore size distributions. This model predicts well the effective excess charge density for all pore size distributions under the thin double layer assumption.