The composition and thickness of multilayered films of poly(acrylic acid) (PAA)/(poly(4-vinylpyridine)/poly(allylamine hydrochloride)) (P4VP/PAH), were analyzed. It is found that the thickness of these film decreases gradually when the fraction of P4VP in the blend solution is decreased. The PAA/PAH multilayers can be crosslinked to form amide bonds between carboxylic acid and amine functionalities of the polyelectrolytes. Atomic force microscopy (AFM) was used to monitor the induced morphological changes in blended thin film assembled from solutions with different P4VP/PAH compositional ratios. The results show that the composition and thickness of these films of PAA/(P4VP/PAH) can be varied by changing the composition of blend adsorption solution.