Molecular dynamic rearrangement in a Langmuir (L) film of zinc stearate in a cross section image has been analyzed by employing polarization modulation infrared reflection spectrometry (PM-IRRAS) and X-ray absorption fine structure (XAFS). The number of coordination on a zinc cation is evaluated by XAFS, and the coordination structure of the carboxylic group is revealed by the IR analysis. An L film prepared at a fixed area without using film-compression bar exhibits time-dependent change of the coordination structure about a zinc cation, and it attains a highly ordered coordination structure in the carboxylic group region. However, an L film prepared by the Langmuir technique using a compression bar exhibited ignorable spectral changes in both IR and X-ray analyses. The hydrocarbon chains in the compressed L film are better uniformed than the uncompressed film, but the uniformed molecular arrangement of the carboxylic group is restricted to be rearranged, and it does not attain a stable structure in terms of coordination on the zinc cation.