PbTiO3 films were prepared by rf magnetron sputtering at various sputtering conditions. It was found that the composition of deposited films is strongly dependent on the sputtering gas pressure and the gas ratio of Ar/O2, and that the crystal orientation of the film is decided by the substrate, the substrate temperature and the target composition. A-axis oriented PbTiO3 film was fabricated on the substrate of the quartz glass where tensile stress occurred against the film. During the sputtering, plasma spectra of PbTiO3 were measured by optical emission spectroscopy. Pb vaporization from the substrate could be observed by this method, and consequently the formation mechanism of PbTiO3 film was investigated.