In the present work, the interaction mechanism of specific polyelectrolyte multilayers (PEMs), fabricated by layer-by-layer deposition of polydiallyldimethylammonium chloride (PDDA) and poly(sodium 4-styrenesulfonate) (PSS), is studied using atomic force microscopy. The underwater oil-repellency of PSS-capped PEMs was further explored by measuring the interaction forces between tetradecane droplets and PEMs-coated silica substrates under various salinities. The force curves were analyzed following the Stokes–Reynolds–Young–Laplace theoretical model. Desirable consistency was achieved between the experimental and theoretical calculations at low NaCl concentrations (0.1 mM and 1 mM); however, underestimation of the attractive force was found as the NaCl concentration increases to moderate (10 mM) and high (100 mM) levels. Discrepancy analyses and incorporated features toward a reduced surface charge density were considered based on the previous findings of the orientation of anionic benzenesulfonate moieties (Liu et al. in Angew Chem Int Ed 54(16):4851–4856, 2015. https://doi.org/10.1002/anie.201411992). Short-range steric hindrance interactions were further introduced to simulate “brush” effect stemming from nanoscale surface roughness. It is demonstrated in our work that the PSS-capped PEMs remains a stable underwater lipophobicity against high salinity, which renders it potential application in surface wetting modification and anti-fouling.