The preparation of urea (bonded) cross-linked multilayer thin films by sequential deposition of bifunctional and tetrafunctional molecular building blocks is demonstrated. Multilayer growth as a. function of deposition cycles was inspected using UV-Vis absorption spectroscopy.. From infrared results, three characteristic infrared bands of amide I, amide II, and asymmetric v(a)(N-C-N) strtching confirmed the formation of polyurea networks by alternate dipping into solutions of amine and isocyanate functionality monomers. The deconvoluted component of the C is and N is spectra obtained by X-ray photoelectron spctroscopy shows clear evidence of stable polyurea networks. The enhancement of structural periodicity with film growth was demonstrated by grazing incidence small-angle X-ray scattering measurements. The thin film near the substrate surface seems to have an amorphous structure. However, molecular ordering improves in the surface normal direction of the substrate with a certain number of deposited layers. Constant mass density was not observed with deposition cycles. The mass density increased up to 16% within deposited layers from proximate layers to those extending away from the substrate surface. This difference in the packing density might derive from the different degrees of cross-linking among layers proximate to the substrate surface and extending away from the substrate surface.