Infrared multiple-angle incidence resolution spectroscopy (IR MAIRS) has been employed for the structural analysis of a heterogeneous multilayer Langmuir-Blodgett (LB) film of ketomycolic acid (keto-MA). Keto-MA was chosen for the study because the molecule changes its conformation largely, which depends on the layer structure of the LB film: the long alkyl chain with a keto group remains folded when it has no counter layer for interdigitation. IR MAIRS is a surface analytical technique that was originally developed to analyze anisotropic structure in a thin film prepared on an IR transparent material. In the present study, however, a newly found characteristic of MAIRS has been used to discuss the molecular conformation and the interdigitation architecture between two adjacent monolayers. As expected theoretically, the molecular folding was clearly detected as 'IR MAIRS shift'. Subtraction of the IR MAIRS spectra of single- and triple-monolayer LB film of keto-MA yielded unambiguous results for the interdigitated double layer in the triple-monolayer LB film, and the layer sequence was also revealed.