We have probed the TiO2-mediated photomineralization of Langmuir-Blodgett (LB) films of stearic acid via atomic force microscopy (AFM) and FT-IR. In situ AFM images revealed that at the submicrometer level the photodecomposition process of stearic acid molecules on a polycrystalline anatase TiO2 film is inhomogeneous, with the various reaction initiation centers or nucleation regions being randomly distributed throughout the photocatalyst surface. Furthermore, parallel FT-IR results showed that the reaction follows pseudo-first-order kinetics. To rationalize the observed random LB film photoetching and buckling behavior, we invoked a simple reaction model that incorporates the reactivity of the TiO2 film and LB film disorganization phenomenon during the photodegradation process.