Direct alpha-hydroxylation of ketones using molecular oxygen was accomplished by organic-inorganic hybrid polymers. A newly prepared Cu-piperazine hybrid polymer was tolerant to the basic conditions, and with employment of lithium hydroxide smoothly catalyzed the alpha-hydroxylation of ketones. In the present catalytic process not only tetralone derivatives, but also acyclic ketones were converted to the alpha-hydroxy ketones in good yield.