A chemical approach to atomic layer deposition (ALD) of oxide thin films is reported here. Instead of using water or other compounds for an oxygen source, oxygen is obtained from a metal alkoxide, which serves as both an oxygen and a metal source when it reacts with another metal compound such as a metal chloride or a metal alkyl. These reactions generally enable deposition of oxides of many metals. With this approach, an alumina film has been deposited on silicon without creating an interfacial silicon oxide layer that otherwise forms easily. This finding adds to the other benefits of the ALD method, especially the atomic-level thickness control and excellent uniformity, and takes a major step toward the scientifically challenging and technologically important task of replacing silica as the gate dielectric in the future generations of metal oxide semiconductor field effect transistors.