A novel concept of utilizing electro-optical active oxides in silicon photonic devices is developed and realized in the frame of this thesis. The integration of such oxides extends the silicon photonics platform by non-linear materials, which can be used for ultra-fast switching or low-power tuning applications. Barium titanate is used as active material as it shows one of the strongest Pockels coefficients among all oxides. Three major goals are achieved throughout this work: First, thin films of BaTiO3 are epitaxially grown on silicon substrates via molecular beam epitaxy (MBE) using thin SrTiO3 buffer layers. A shuttered co-deposition growth technique is developed in order to minimize the formation of defects in the BaTiO3 films by achieving a 1:1 stoichiometry between barium and titanium. The layers show a tetragonal symmetry and are therefore well-suited for electro-optical applications. The orientation of the long c -axis of the BaTiO3 crystal can be tuned to point perpendicular or parallel to the film surface, depending on the growth conditions. In addition, thin MBE-grown seed layers are combined with rf-sputter deposition. With this hybrid growth approach, rather thick ( > 100 nm), epitaxial BaTiO3 layers on silicon substrates are obtained with a commercially available, wide spread deposition technique. As a second goal, a strong Pockels coefficient of reff = 148 pm/V is determined in the epitaxial BaTiO3 films. This first experimental result on the electro-optical activity of BaTiO3 layers on silicon shows a clear enhancement compared to alternative non-linear materials such as lithium niobate with reff = 31 pm/V. By means of the electro-optical characterization method, also the presence of ferroelectricity in the films is demonstrated. Third, the electro-optical active BaTiO3 layers are embedded into silicon photonic devices. For this purpose, a horizontal slot-waveguide structure with a ~50 nm-thick BaTiO3 film sandwiched between two silicon layers is designed. With this design, the optical confinement in the active BaTiO3 layer is enhanced by a factor of 5 compared to Si-waveguide structures with a standard cross section and BaTiO3 as cladding. Straight BaTiO3 slot-waveguides with propagation losses of 50 − 100 dB/cm as well as functional passive devices such as Mach-Zehnder-interferometers, couplers, and ring resonators are experimentally realized. Additionally, first active ring resonators with Q-factors of Q~5000 are fabricated. The physical origin of the observed resonance shift as a function of the applied bias voltage, however, can not be conclusively clarified in the present work. The combination of high-quality, functional BaTiO3 layers with silicon photonic devices as demonstrated in this thesis offers new opportunities by extending the design palette for engineering photonic circuits with the class of electro-opticalactive materials. The integration of oxides such as BaTiO3 enables novel device concepts for tuning, switching, and modulating light in extremely dense photonic circuits. The integration also opens exciting challenges for material scientists to tailor the electro-optical properties of those oxides by strain engineering or fabrication of superlattice structures, which could ultimately lead to another boost of their electro-optical properties.