To further investigate the morphological evolution of SVA with NPG dopant, SEM observations on the etched SVAs were performed. Figures show the SEM micrographs of SVA doped with NPG after removing PLA domains. In eSVA/N5, disordered pores can be observed (Figure ), rather than cylinder phase observed in eSVA/N0 (see Figure ). Also, as the doping concentration exceeds 30%, a lamellar morphology can be observed due to the collapse and compression of the phase structure after removing the PLA domains (Figure ). Moreover, when the concentration of NPG is higher than 70%, inversed cylinder structures can be observed (Figure ). To confirm whether the NPG dopant additive was completely removed during etching, etched SVA/NPG composites were examined by 1 H NMR. It is confirmed that most of NPG can be removed within 1 hour (Figure ). In addition, the morphologies of selfassembled SVA/NPG composites before and after etching were examined by SAXS. It is observed that the intensity of SAXS peaks is enhanced after etching (Figure ). In particular, the etched SVA/NPG composites exhibited broad scattering peaks, which is consistent with the disordered morphologies observed in TEM and SEM. However, it is challenging to determine the structures according to the SAXS results, due to the broad scattering peaks. To gain a deeper insight into the mechanism on the controlled self-assemblies of SVA, FTIR spectroscopy is used to determine the inter-molecular interactions between SVA and NPG. Figure shows the FTIR curves of SVA, NPG, and SVA/N10 before and after etching. In the FTIR spectrum of SVA, the peak at round 993 cm -1 is associated with the stretching mode of the pyridine rings. However, this peak is significantly weakened in the presence of NPG. Also, the stretching band of pyridine rings shifts to the higher wavenumber , due to the coordination of NPG with pyridine rings. For the same reason, the characteristic peaks of NPG at 2971, 2928, and 2882 cm -1 are not visible in SVA/N10. The above results indicate that, in the SVA/NPG composites, the diol molecules interact with the pyridine rings of P4VP mid-segments through hydrogen bonding (Scheme 1). Consequently, the block copolymers were 'noncovalently' crosslinked by the diols, resulting in the reduced chain mobility and reduced kinetics of microphase separation. It leads to the generation of long-lived metastable phase with network morphologies during solution casting. After selective etching, mesoporous bulks with bicontinuous channels and grafted P4VP segments on the inner pore walls can be achieved. Scheme 1. Mesoporous materials with disordered bicontinuous channels from controlled self-assembly of PS-P4VP-PLA triblock copolymer.