A series of diblock-copolymers were synthesized through anionic polymerization of styrene and tert-butyl methacrylate (tBuA) with different monomer ratios, and analogous block-copolymeric derivatives (PS-b-PAA)s with monofunctional carboxylic acid groups were obtained by further hydrolyzation as hydrogen-bonded (H-bonded) proton donors. Via H-bonded interaction, these diblock-coplymeric donors (PS-b-PAA)s were incorporated with luminescent mono-pyridyl/bis-pyridyl acceptors to form single/double H-bonded supramolecules, that is, H-bonded side-chain/cross-linking copolymers, respectively. The supramolecular architectures formed by donor polymers and light-emitting acceptors were influenced by the ratio of acid blocks in the diblock copolymeric donors and the type of single/double H-bonded light-emitting acceptors. Their thermal and luminescent properties can be adjusted by H-bonds, and more than 100 nm of red-shifted photoluminescence (PL) emissions were observed, which depend on the degrees of the H-bonding interactions. Self-assembled phenomena of amphiphilic dibolck copolymers and their H-bonded complexes were confirmed by TEM micrographs, and supramolecular microphase separation of spherical micelle-like morphology was demonstrated to affect the photophysical properties. Polymer light-emitting diode (PLED) devices containing H-bonded complexes showed electroluminescence (EL) emissions of 503-560 nm under turn-on voltages of 7.5-9.0 V, maximum power efficiencies of 0.23-0.37 cd/A (at 100 mA/cm(2)), and maximum luminances of 318-519 cd/m(2) (around 25 V). (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4685-4702, 2009