The crystallographic properties of BaTiO 3 thin films, grown by pulsed laser deposition on MgO substrates, were found to be strongly influenced by the oxygen pressure used during growth. Low pressure grown films were c-oriented while increasing oxygen pressure produced films with preferred a-orientation. The crystal reorientation resulted in the shift of optical birefringence from +0.04 to −0.025 with low levels of birefringence in films possessing low tetragonal distortion. Mach-Zehnder electro-optic waveguide modulators were fabricated to characterize the electro-optic properties of the deposited films and to evaluate the suitability of these films for planar optical applications. An effective electro-optic coefficient of 23 pm/V was obtained for a c-axis oriented film near the crystal c→a reorientation point.