Block copolymer (BCP) self-assembly produces chemically and topographically patterned surfaces which are used to guide the formation of Cu nanostructures by exploiting differences in the mobility of vapordeposited species on each microdomain. Cu metal films a few nm thick were deposited on three different BCP surfaces self-assembled from poly(styrene-b-methyl methacrylate) (PS-b-PMMA) and polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP). For PS-b-PMMA, the effects of chemical heterogeneity dominate over the effects of the 2 nm peak-to-valley topography, and sputtered Cu preferentially wets the PS block. PS-b-P2VP has greater chemical and topographical contrast and shows a wider process window for selective deposition. Cu grown by evaporation has less surface mobility, and shadowing effects are believed to dominate pattern formation. The hierarchical self-assembly process of thin metal films on BCP surfaces provides a route to fabricating heterogeneous metallic nanostructures.