The present study demonstrates the hydrophobic effect of poly(electrolyte) multilayer films when they are alkyl-grafted and complexed or not with surfactants. For this purpose, sodium hydrophobically modified poly(acrylates) (PAC(n)Na, n = 10, 18) or their anionic complexes with alkyltrimethylammonium bromides (C(X)TAB, x = 10, 12, 14, 18), and the cationic poly(diallyldimethyldiammonium chloride) (PDDAMAC) are assembled by layer-by-layer deposition on a glass substrate. Contact angle (CA) measurements reveal that films constructed with PAC(n)Na-C(x)TAB/PDADMAC are superior water repellants than those of PACnNa/PDADMAC. For example, the highest CA is obtained for the PAC(18)Na-C(18)TAB/PDADMAC. Moreover, it has been observed that the CA increases with the alkyl chain length of PACnNa and of surfactant. The film roughness and thickness have the same trend as wettability. Thinner and less coarse films are obtained by NaCl addition, as witnessed by SEM and AFM. (C) 2016 Elsevier B.V. All rights reserved.