This contribution presents a study of the atomic and electronic structure of the (√5×√5)R26.6° surface reconstruction on BaTiO3 (001) formed by annealing in ultrahigh vacuum at 1300 K. Through density functional theory calculations in concert with thermodynamic analysis, we assess the stability of several BaTiO3 surface reconstructions and construct a phase diagram as a function of the chemical potential of the constituent elements. Using both experimental scanning tunneling microscopy (STM) and scanning tunneling spectroscopy measurements, we were able to further narrow down the candidate structures, and conclude that the surface is either TiO2-Ti3/5, TiO2-Ti4/5, or some combination, where Ti adatoms occupy hollow sites of the TiO2 surface. Density functional theory indicates that the defect states close to the valence band are from Ti adatom 3d orbitals (≈1.4  eV below the conduction band edge) in agreement with scanning tunneling spectroscopy measurements showing defect states 1.56±0.11  eV below the conduction band minimum (1.03±0.09  eV below the Fermi level). STM measurements show electronic contrast between empty and filled states’ images. The calculated local density of states at the surface shows that Ti 3d states below and above the Fermi level explain the difference in electronic contrast in the experimental STM images by the presence of electronically distinctive arrangements of Ti adatoms. This work provides an interesting contrast with the related oxide SrTiO3, for which the (001) surface (√5×√5)R26.6° reconstruction is reported to be the TiO2 surface with Sr adatoms.