Abstract A mathematical expression describing the growth regime of multilayers formed layer by layer and the correlation between the nature of the growth process and the distribution of the charges in the polyelectrolyte deposited on the surface of the film is reported. Two typical polyelectrolyte pairs were chosen such that one of them causes the film to grow linearly while the other causes the film to grow exponentially. The growth processes were monitored by UV‐Vis spectrophotometry and the experimental data was analyzed. The influence of the polyelectrolyte and NaCl concentration on the fabrication of PAH/PSS and PDDA/PSS films is discussed by analyzing the change of model parameters. magnified image