The phase behaviors of a polydimethylsiloxane-b-poly(2-vinylpyridine) block copolymer (PDMS-b-P2VP, DV) tuned by the supramolecular self-assembly approach with the 1-pyrenebutyric acid (PBA) as additive were investigated. The PDMS-b-P2VP block copolymer (D10kV12.5k, the molecular weight of the PDMS and P2VP were 10000 and 12500 g mol(-1), respectively) with volume fraction of P2VP (f(P2VP)) 52% exhibited hexagonally perforated layer (HPL) morphology after dried from the solution, and the nanostructure transformed to gyroid structure after thermal annealing above 140 degrees C, which were indicated by the small-angle X-ray diffraction (SAXS) and transmission electron microscopy (TEM) results. Through solution blending method, a series of H-bonding supramolecular complexes of PDMS-b-P2VP with PBA were fabricated. The Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC) experiments demonstrated that the PBA molecules uniformly interacted with P2VP through H-bonding and the glass transition temperature of P2VP(PBA)(x) decreased with the increase of the mole ratio (x) of PBA/2VP. Due to the increase of the volume fraction of P2VP(PBA)(x) and that of the stretching extent of the P2VP backbone as the x value increased, the microphase-separated nanostructures transformed from HPL to hexagonally packed cylinder (HEX), then to body centered cubic (BCC) structure and then to disordered spheres morphologies. When the PDMS-b-P2VP(PBA)(x) complexes were heated above 120 degrees C, the H-bonding between the P2VP and PBA was broken and the PBA became compatible within both PDMS and P2VP domains and thus the nanostructure of the PDMS-b-P2VP(PBA)(x) complexes transformed accordingly. Therefore, a variety of the nanostructures and structural transformations were induced by the H-bonding formation and disassociation based on one block copolymer. (C) 2018 Elsevier Ltd. All rights reserved.