Optically active films were built up from poly(allylamine hydrochloride) (PAH) and R-(+)--phenylethylamine derivatives of poly(ethylene-alt-maleic acid) (PEMA-PEA) with substituting degrees (DS) ranging from 0.48 to 0.97. The growth of the film was monitored with the circular dichroism (CD) and the UV spectrophotometer and the effect of DS of PEMA-PEA on the film was investigated. UV and CD data show the growth regime of the multilayer changing from exponential to linear. Deposition amounts of PEMA-PEA in multilayer films decrease with the increase in DS of PEMA-PEA, which was explained based on the conformation of the polyelectrolyte and the charge overcompensation as the polyelectrolyte was deposited on the surface of the film. These results are of benefit to the development of multilayer films for the chiral separation of enantiomers.