Rod-coil block copolymers (BCPs) can self-assemble into nanostructures that are useful for the fabrication of nanodevices. However, BCPs are generally difficult to self-assemble into highly ordered nanostructures due to their low chain mobility and strong rod-rod interaction. A facile approach is developed to achieve rapid self-assembly of rod-coil BCPs by blending them with selective additive and annealing in vacuum. Poly(diethyl hexyl oxy-p-phenylene vinylene)-b-poly(methyl methacrylate) (DEHPPV-b-PMMA or PVM) was used as a model copolymer to validate this approach. By adding 30 wt% of a rod-selective additive, p-phenylene vinylene (PV), into the PVM containing 67% (v/v) PMMA, the copolymer can easily self-assemble into lamellae structure at 150 degrees C for 1.5hr under 0.05 torr. This is a significant improvement over the 200 degrees C for 60 h for the sample without additive and vacuum annealing. This energy conservation process should have broad application in the fabrication of highly ordered nanostructure using BCPs. (C) 2018 Elsevier Ltd. All rights reserved.