Azobenzene (Az) derivatives with a urea headgroup, n-{4-[(4-hexylphenyl)azo]phenoxy}alkylurea (6Azn-urea, n = 3, 4, 5, 6, and 7), were synthesized. The characteristics of mono- and multilayers of a series of 6Azn-urea compounds were investigated by means of surface pressure-area isotherm and compressibility measurements, UV-visible and infrared absorption spectroscopy, and X-ray diffraction measurements. Various types of odd-even effects were observed in the spreading behavior and rheological properties in the Langmuir monolayer on the water surface, in the transfer behavior from the water surface to a solid substrate, in the packing state in terms of molecular tilt and Az aggregation in the deposited mono- and multilayers, and in the nature of hydrogen bonding in the multilayers. The carbon parity nature in the 6Azn-urea monolayer should result from the firm fixation at the terminal urea headgroup via intermolecular bifurcated hydrogen bonding, which resembles the situation of self-assembled monolayers attached covalently onto a solid substrate.