Synthesis of diamond thin-films has been tried by an ArF excimer laser-induced chemical vapor deposition (LCVD) technique, using acetylene diluted with hydrogen as a source gas and a silicon wafer as a substrate. In these experiments, irradiation geometry, substrate temperature and laser power density were varied. Upon irradiation by a focused laser beam, deposition of diamond on substrates heated above 400°Cwas observed, and was confirmed by reflection electron diffraction (RED) photographs. Homogeneity of the diamond films was improved by irradiation parallel to the substrate. These facts suggest that the formation of diamond proceeds through multiple photon decomposition of the reactant gas, and that electronic excitation of gas phase rather than that of substrate or adsorbate layer is essential to form diamond.