Scanning tunneling microscopy has been used to identify the adsorption site of H(2)O on TiO(2)(110)-(1 x 1) at 150 K, and to monitor the site of the dissociation products at 290 K. Water adsorbs onto the rows of fivefold coordinated Ti atoms at 150 K, dissociating by 290 K to form bridging but not terminal hydroxyls. This points to the involvement of bridging O vacancies in the dissociation pathway.