Titanium oxide (TiO 2) has been widely used in many fields, such as photocatalysis, photovoltaics, catalysis, and sensors, where its interaction with molecular H 2 with TiO 2 surface plays an important role. However, the activation of hydrogen over rutile TiO 2 surfaces has not been systematically studied regarding the surface termination dependence. In this work, we use density functional theory (PBE+U) to identify the pathways for two processes: the heterolytic dissociation of H 2 as a hydride-proton pair, and the subsequent H transfer from Ti to near O accompanied by reduction of the Ti sites. Four stoichiometric surface orientations were considered: (001), (100), (110), and (101). The lowest activation barriers are found for hydrogen dissociation on (001) and (110), with energies of 0.56 eV and 0.50 eV, respectively. The highest activation barriers are found on (100) and (101), with energies of 1.08 eV and 0.79 eV, respectively. For hydrogen transfer from Ti to near O, the activation barriers are higher (from 1.40 to 1.86 eV). Our results indicate that the dissociation step is kinetically more favorable than the H transfer process, although the latter is thermodynamically more favorable. We discuss the implications in the stability of the hydride-proton pair, and provide structures, electronic structure, vibrational analysis, and temperature effects to characterize the reactivity of the four TiO 2 orientations.