We report on the formation of hierarchical nanostructures of Au, PtOx, FexOy and PdOx using a hybrid technique by combining laser interference ablation (LIA) and block copolymer phase separation (BCPS). Different types of hierarchical arrays can be obtained including square, triangular, linear and circular arrays by varying the loading time of the block co-polymer with metallic salts, and the laser interference technique. The primary ordering of the as-generated nanoarrays (30–100 nm) is tunable by changing either the composition of the block copolymer spun from solution or by changing other parameters that affect the phase separation kinetics of the block copolymer, while the secondary ordering of the features can be tuned from 200 nm to 2 μm, by changing the angle of convergence of the laser beams on the patterned substrate. Such a robust method can be applied to the fabrication of other metallic and ceramic materials including Ag, Co, and Ni (O) and has potential use in the large scale fabrication of hierarchical arrays of catalysts that can be used to grow germanium, silicon nanowires using the vapour–liquid–solid growth (VLS) technique. The as-generated arrays can also find use in optical as well as sensor applications for biodetection and biosensing.