Thin films of Sr0.5Ba0.5TiO3have been grown on MgO (100), SrTiO3(100), and LaAlO3(012) substrates using pulsed laser deposition. These films were characterized by a variety of x‐ray diffraction techniques. Deposited films exhibited true single crystal morphology. X‐ray rocking curves for the (002) reflection as measured by double and triple crystal spectrometers showed unusually narrow full width at half‐maximum (FWHM) values of 72 arcsec for films grown on LaAlO3, and 140 arcsec for films deposited onto SrTiO3. The FWHM for films deposited on MgO were significantly broader (∼2500 arcsec). While the quality of the epitaxial films is related to the lattice mismatch between the film and the substrate, extremely well aligned films can be grown on substrates with a relatively large lattice mismatch.