BaTiO3 is a versatile material that finds applications in sensors and electrooptical devices. Interactions start at the very surface, thus it is necessary to understand at a fundamental level its geometrical and electronic structure. Ferroelectricity is a key property that provides unique opportunities to explore molecular adsorption at a surface and allows investigation of chemical interactions as well. Interaction with gaseous species can be performed in-situ in "as-received" and poled crystals by controlling the poling voltage at the surface. Recent studies with macroscopic measurements show that polarization indeed affects molecular adsorption but mechanisms are not yet understood. Here we present scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) of atomically resolved reconstructions on BaTiO3 (001) surfaces, (√5x√5)R26.6^o. A comparison of electronic structure determined by STS with theoretical calculations shows that the surface that is Ti terminated. In this and other reconstructions Ti-ad atoms create filled and empty states that are imaged in STM. The interactions of reconstructed surfaces with H2O is examined with atomic resolution. This is the first atomic scale observation of molecular adsorption on a ferroelectric surface.