This study deals with selective separation of mono- and divalent cations from aqueous salt solutions using polymeric films based on polyethylene (PE) and polyamide6 (PA6), and two different commercial nanofiltration (NF) membranes. The diffusion rates (D) of ions (Na+ and Ca2+) , separation factors (alpha) and ion rejections (R) of the films and NF membranes are examined comparatively as well as their surface morphology and hydrophilicity. It is observed that the diffusion rates of Na+ are in the range of 0.7-1.8 x 10(-8) cm(2).s(-1) in the decreasing order of PE > NF90 > NF270 > PA6 while Ca2+ shows diffusion rates of 7.4-18.4 x 10(-8) cm(2).s(-1) in the increasing order of NF270 > NF90 approximate to PA6 > PE. Rejection values of the polymeric films and NF membranes against to Na+ and Ca2+ vary between 90% and 99.6%.The highest alpha (Ca2+/Na+) is found to be 20 for PA6 film D, alpha, and R value of both polymeric films and NF membranes are strongly affected by the existence of osmosis during diffusion-dialysis and the sizes of hydrated sodium and calcium ions. In conclusion, the film based on PA6 may be a good alternative for selective separation of mono- and divalent cations.