Precursor and process design for photo-assisted metal atomic layer deposition (ALD) and chemical vapor deposition (CVD) is described. In an example, a method of fabricating a thin metal film involves introducing precursor molecules proximate to a surface on or above a substrate, each of the precursor molecules having one or more metal centers surrounded by ligands. The method also involves depositing a metal layer on the surface by dissociating the ligands from the precursor molecules using a photo-assisted process.