Using small-angle X-ray diffraction, we demonstrate in this Letter that alternate-layer Langmuir-Blodgett films of tricosanoic acid/1-docosylamine and docosanoic acid/1-docosylamine retain their ‘as-deposited’ structure. Both of these non-centrosymmetrical bilayer structures exhibit a smaller tilting of their hydrocarbon tails than that observed for the corresponding centrosymmetric monocomponent systems. The electron-density profiles obtained for the alternate-layer systems reveal that the points of contact for the ends of the hydrocarbon chains are shifted from the centre of the unit cell and that the density maxima, corresponding to the positions of the polar head groups, possess an asymmetrical shape.