The influence of BaTiO(3) ferroelectric domain orientations for high efficiency electro-optic modulation has been thoroughly analyzed. The Mach-Zehnder modulator structure is based on a CMOS compatible silicon/BaTiO(3)/silicon slot waveguide that supports both TE and TM polarizations whereas the Pockels effect is exploited by the application of a horizontal electric field with lateral electrodes placed on top of the BaTiO(3) layer. The influence of the waveguide parameters has been optimized for each configuration and the lowest V(π) voltage combined with low losses has been determined. A V(π)L as low as 0.27 V·cm has been obtained for a-axis oriented BaTiO(3) and TE polarization by rotating the waveguide structure to an optimum angle.