Laser-ablated Sc atoms have been reacted with water molecules during condensation with argon at 11 K. In agreement with previous thermal atom reactions, absorptions at 1482.6 and 713.0 cm(-1) are assigned to the HScOH molecule formed via an insertion reaction. Photolysis of the HScOH produces the metal monoxide ScO. In addition, new absorption at 765.6 cm(-1) is also observed and is assigned to the ScOH molecule. The ScOH molecule undergoes photoinduced rearrangement to the HScO molecule, which is characterized by Sc-II and Sc-O stretching vibrations at 1391.1 and 922.3 cm(-1). Density functional theoretical calculations have been performed for the aforementioned species, and important transition states on the reaction paths have been obtained.