Atomically engineered oxide multilayers and superlattices display unique properties responsive to the electronic and atomic structures of the interfaces. We have followed the growth of ferroelectric BaTiO3 on SrRuO3 electrode with in situ atomic scale analysis of the surface structure at each stage. An oxygen-induced surface reconstruction of SrRuO3 leads to formation of SrO rows spaced at twice the bulk periodicity. This reconstruction modifies the structure of the first BaTiO3 layers grown subsequently, including intermixing observed with cross-section spectroscopy. These observations reveal that this common oxide interface is much more interesting than previously reported and provide a paradigm for oxygen engineering of oxide structure at an interface.