Accumulated Langmuir-Blodgett (LB) films that consist of two layers of barbituric acid (BA) and triaminotriazine (TAZ) derivatives (C(18)BA and 2C(18)TAZ) were deposited at various surface pressures on a gold-evaporated glass slide covered with a deuterated cadmium stearate (CdSt-d(35)) monolayer. The two-monolayer LB films (the CdSt-d(35) layer is considered to be a part of the substrate) were measured by infrared reflection-absorption (IRRA) spectrometry to investigate the hydrogen-bonding network formed between the two layers. The most notable results were given by the LB film that has the layer configuration of IR// C(18)BA/2C(18)TAZ/CdSt-d(35)/Au. The C(18)BA layer was deposited at various surface pressures on the 2C18TAZ monolayer. Depending on the surface pressure, the wavenumber of the C=O stretching vibration band ((C=O)), derived from BA, showed drastic change. At 20 mN m(-1), the C=O groups were found to be in non-hydrogen bonded state (1755 cm(-1)) to a large extent. The non-hydrogen bonded C=O groups are, in general, rarely seen for the interacted BA/TAZ system. The extraordinary non-hydrogen bonded C=O groups were explained readily by a novel schematic model that was estimated through the molecular orientational analysis. In consequent, the film-to-film interaction is found to give a quite unique hydrogen bonding network structure.