A novel dual-responsive core-shell type hybrid inclusion complex composed of an azobenzene-terminated copolymer PNIPAM-b-PAA and beta-cyclodextrin-modified silver/polydiacetylene (beta-CD@Ag/PDA) nanocrystals had been fabricated based on the host-guest interaction between azobenzene unit in the block copolymer and beta-CD cavities on the surface of the hybrid nanocrystals. While the hybrid nanocrystals provide necessary nonlinear optical properties, the copolymer shells exhibit dual sensitivity to temperature and pH variation. The dual stimuli-responsive behavior of the copolymer shells was used to act as the driving force to adjust the relative spatial distances between neighboring hybrid nanocrystals, further controlling the localized surface plasmon resonance enhancement and the corresponding NLO effect. It is expected that this research will introduce a new way for preparing novel smart NLO materials. (C) 2012 Elsevier Ltd. All rights reserved.