We studied the adsorption of water, methanol, and formic acid at terraces and steps on the stoichiometric anatase TiO2(101) surface by means ofdensity functional theory calculations. Our results show that the reactivity of the step edges is distinct from that of the (101) terraces and is insteadsimilar to the reactivity of the extended (112) and (100) surfaces, which are exposed at their facets. More specifically, on the (101) terraces, allmolecules are adsorbed in molecular (undissociated) form, and the adsorption energy is rather low (<1 eV). At step D-(112), adsorption energiesare significantly larger than on (101) terraces, but molecular adsorption is still favored by water and methanol. At step B-(100), all of the moleculesprefer to dissociate, even though the adsorption energy of water is lower than on the (101) terrace. The connection between reactivity and localstructure is highlighted, and comparison with available experimental data is provided.