InP and In‐oxide films have been deposited on quartz, GaAs, and InP substrates by excimer laser induced photodecomposition of (CH3)3InP(CH3)3and P(CH3)3vapors at 193 nm. The oxide film refractive index and stoichiometry are close to In2O3. Phosphorus incorporation in the films was greatly enhanced by focusing the laser beam to promote multiple‐photon dissociation processes. These conditions also lead to enhanced carbon inclusion in the films, due to formation of species such as CH and CH2in the gas phase. However, this carbon inclusion could be suppressed by focusing the beam onto the surface at normal incidence. In the irradiated zone InP could be deposited with P(CH3)3‐to‐(CH3)3InP(CH3)3ratios of only ∼1:1. The technique offers several potential advantages over conventional metalorganic chemical vapor deposition, including lower temperature, enhanced rates, safer gases, and three‐dimensional film composition control. Strong atomic In emission is observed in the gas phase above the depositing film, due to a multiple photon dissociation process. Gas phase fluorescence from P, CH, and C was also observed. These emissions give insight into the photodecomposition mechanism and also serve as a monitor of metalorganic precursor concentrations.