Rylene bisimide-based nanoparticles with cross-linked core were synthesized by site-selective crosslinking and self-assembly of block copolymer composed of poly(N-vinyl amine) and poly(N-isopropylacrylamide), which was prepared by RAFT polymerization. Single-step imidization of poly(vinyl amine)-b-poly(NIPAM) with arylene dianhydride derivatives, including naphthalene-1,8:4,5-tetracarboxylic dianhydride and perylene-3,4:9,10-tetracarboxylic dianhydride, afforded nanoparticles with naphthalene bisimide core (NP-NBI) and perylene bisimide core (NP-PBI), respectively. DLS analysis demonstrated that the size of cross-linked nanoparticles was uniform and could be controlled by the imidization conditions. UV-vis, fluorescence, and cyclic voltammetry measurements led to the optical and electrochemical properties derived from NBI and PBI units in the cross-linked nanoparticles, supporting the successful preparation of desired nanoparticles. (C) 2015 Elsevier Ltd. All rights reserved.