Methods for selective deposition, and structures thereof, are provided. Material is selectively deposited on a first surface of a substrate relative to a second surface of a different material composition. A passivation layer is selectively formed from vapor phase reactants on the first surface while leaving the second surface without the passivation layer. A layer of interest is selectively deposited from vapor phase reactants on the second surface relative to the passivation layer. The first surface can be metallic while the second surface is dielectric, or the second surface is dielectric while the second surface is metallic. Accordingly, material, such as a dielectric, can be selectively deposited on either metallic or dielectric surfaces relative to the other type of surface using techniques described herein. Techniques and resultant structures are also disclosed for control of positioning and shape of layer edges relative to boundaries between underlying disparate materials.