2014 Wiley Periodicals, Inc. The reported diblock brush terpolymer displays the fundamental advantages of high macromolecular and regiochemical control in simultaneous top-down/bottom-up construction of advanced positive-tone photoresist materials. By selective partition the substrate adhesion, surface-active migration, and chemically-reactive deblocking functional compositions into the cylindrical polymer brush architectures, large-areas of vertical alignment of the polymers within thin films are realized. The bottom-up premeditated system enables effective top-down lithography to produce near-molecular pixel resolution (2-3 molecules) at low operation dosage.