Metallic layers can be selectively deposited on surfaces of a substrate relative to a second surface of the substrate. In preferred embodiments, the metallic layers are selectively deposited on copper instead of insulating or dielectric materials. In preferred embodiments, a first precursor forms a layer or adsorbed species on the first surface and is subsequently reacted or converted to form a metallic layer. Preferably the deposition temperature is selected such that a selectivity of above about 90% is achieved.