A new styrenic monomer 2-propargyloxy-5vinylbenzaldehyde (PVB) containing both aldehyde and alkyne reactive groups was designed for the synthesis and subsequent orthogonal postfunctionalization of dual-clickable polymer precursor. Reversible addition-fragmentation chain transfer polymerization of PVB afforded a structurally well-defined polymer poly(2-propargyloxy-5-vinylbenzaldehyde) (PPVB) bearing alkyne and aldehyde functionalities that are reactive towards azide-and aminooxy-containing molecules, respectively. Therefore, the resulting PPVB can be served as a dual-clickable polymer scaffold for construction of multiple functional polymers via orthogonal alkyne-azide and aldehyde-aminooxy click reactions. Postpolymerization modification of PPVB sequentially with aminooxy-terminated poly(ethylene oxide) s (H2NO-PEO) and azide-functionalized imidazolium-type ionic liquid (N3-IL-TFSI, having bis(trifluoromethane) sulfonamide, TFSI, counter-anion) yielded an interesting multicomponent graft polymer PPVB-g(PEO-and-IL-TFSI). After anion exchange of hydrophobic TFSI counter-anion by bromide (Br) anion, the resulting graft copolymer PPVB-g-(PEO-and-IL-Br) becomes soluble in water, and its imidazolium units can capture negatively charged tetraphenylethylene disulfonate derivative (TPE-2SO(3)) guest molecule via electrostatic complexation to form in situ self-assembled fluorescent nanoaggregates with colloidal stability imparted by hydrophilic PEO chains. (C) 2017 Wiley Periodicals, Inc.