Langmuir–Blodgett (LB) films of Cd arachidate and Ca arachidate with thicknesses of 1, 3, 9, and 25 layers were investigated using near edge x-ray absorption fine structure (NEXAFS spectroscopy), small angle x-ray scattering (SAXS), and reflected high energy electron diffraction (RHEED). The results from the x-ray diffraction experiments on layer thickness and interface roughness complement the structural information from NEXAFS on the average tilt angle of the alkyl chains in real space. The RHEED measurements confirm these findings and give additional information on the lateral order in these organic films. We find that the monolayer film shows a substantial degree of disorder, while for three and more LB layers, the molecular orientation is virtually identical to that of the corresponding fatty acid salts, i.e., the hydrocarbon chains are oriented perpendicular to the substrate surface in an all-trans conformation. Furthermore, a simplified and more robust analysis scheme for NEXAFS data obtained for hydrocarbon chains is presented.