A cleavable trityl ether juncture is introduced between polystyrene (PS) and poly(ethylene oxide) (PEO), and thus highly ordered nanoporous thin films have been prepared from self-assembled PS-b-PEO diblock copolymers, via the removal of PEO from solvent-annealed PS-b-PEO thin films in a simple two or one-step process. When patterned substrates are used, addressable nanopore arrays with a high degree of lateral order and a well-defined lattice orientation can be readily produced (see figure).