The aim of this study was to analyze, both theoretically and experimentally, the material transport mechanisms governing the separation of ionic species in aqueous solutions using nanofiltration membranes. To interpret the experimental results, the Donnan Steric Partitioning Model (DSPM) and the Dielectric Exclusion Model (DSPM-DE) were applied and computationally simulated in Matlab. Experimental tests were conducted using a pilot-scale system with commercial NF90 membranes. The results indicate that the DSPM better describes the rejection of monovalent ions (sodium and chloride), while the DSPM-DE is more suitable for divalent ions (sulfate and magnesium). Additionally, both models were sensitized to explore the impact of hindrance factors on the rejection of different ionic species. For neutral molecules present in the solution, it was observed that the DSPM and DSPM-DE do not adequately interpret selectivity, suggesting that under such conditions, the electrostatic exclusion mechanism loses significance, with the steric mechanism prevailing.