A method of depositing noble metals on a metal hexaboride support. The hexaboride support is sufficiently electropositive to allow noble metals to deposit spontaneously from solutions containing ionic species of such metals onto the support. The method permits the deposition of metallic films of controlled thickness and particle size at room temperature without using separate reducing agents. Composite materials comprising noble metal films deposited on such metal hexaborides are also described. Such composite materials may be used as catalysts, thermionic emitters, electrical contacts, electrodes, adhesion layers, and optical coatings.