Surface functionalization with polyelectrolyte multilayer films (PEM films) has become very popular owing to its simplicity and versatility However, even if some research is already available, this field of surface chemistry lacks a systematic knowledge of how the polyelectrolyte structure and solution conditions influence the growth of PEM films In this investigation, we focus on the possible relationship between turbidity of polycation and polyanion mixtures in solution, and the buildup of PEM films made from the same polyelectrolytes in the same physicochemical conditions, namely pH, temperature and ionic strength It comes out that for six different polycation/polyanion combinations there is a clear correlation between the turbidity evolution of polycation/polyanion complexes with the salt concentration and the evolution of the film deposition with the same parameter. In this investigation, the complexes in solution were prepared in conditions where the ratio between the number of cationic to anionic groups was close to unity Even if there is a correlation between turbidity in solution and PEM film deposition. we found some exceptions in the low salt concentration regime This work is an extension of the preliminary works of Cohen Stuart (D. Kovacevic et al Langmuir 18 (2002) 5607-5612) and Sukishvili et al (S A Sukhishvili, E Kharlampreva and V. Izumrudov, Macromolecules 39 (2006) 8873-8881). (C) 2010 Elsevier Inc. All rights reserved