The room-temperature uptake and reactivity of gas-phase methyl dichlorophosphate (MDCP) and trichlorophosphate (TCP) within trisilanolphenyl-polyhedral oligomeric silsesquioxane (POSS) Langmuir-Blodgett films are investigated. The halogenated phosphate molecules are found to readily diffuse into and react with the hybrid inorganic-organic silicon-oxide films under ambient conditions. Reflection absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), and fast atom bombardmentmass spectrometry (FAB-MS) measurements suggest that the chlorophosphates undergo hydrolysis with the silanol groups of the POSS LB-film. Substitution and elimination reactions appear to cap the corner of the POSS molecules, leaving a surface-bound phosphoryl group and a resulting structure that is highly stable at elevated temperatures.