It is found that the reflection peaks can be observed at a relative q value of 1 : √7 in the pristine SVA. After removing PLA microdomains, more reflection peaks can be observed at relative q values of 1 : √3 : √4 : √7 : √9, due to the enhanced electron contrast. Also, the SAXS results indicate the formation of hexagonally packed cylinders by the self-assembly of SVA. Figure shows the corresponding transmission electron microscopy (TEM) micrograph of SVA stained by I2, in which spot-like patterns with hexagonal symmetry can be observed. By taking a closer look on the TEM micrograph, ring-like morphology can be recognized, resulting from the strained P4VP mid-block (the arrows in Figure ). It indicates that core-shell cylinder structures were formed by pure SVA. Moreover, the corresponding SEM micrograph exhibits typical cylinder structures in the etched SVA (Figure ), which is consistent with the above results. As shown above, after selective etching, porous structure can be achieved. To clarify whether P4VP mid-block was removed during etching, SVA etched for different times were measured by H NMR. As shown in Figure , the peak at around 5.2 ppm is attributed to the methine protons (-CH) of the PLA, while the peak around 8.3 ppm is associated with the protons on the pyridine rings of P4VP. It is found that PLA can be completely removed after etching for 3 hours (Figure ). Yet, the molar fraction of P4VP in the etched SVA is almost independent with the etching time, indicating that P4VP mid-blocks were not cut off from PS matrix during etching. Also, these results confirm the presence of grafted P4VP on the inner surface of mesopores in the etched SVA. Next, we intend to control the self-assembled morphologies of SVA. To this end, three diol molecules, i.e., ethylene glycol (EG), neopentyl glycol (NPG), and bis(4hydroxyphenyl) sulfone (BPS), were doped into SVA by solution mixing. In the following study, the composites of SVA doped with NPG/EG/BPS are termed as SVA/Nx, SVA/Ex, and SVA/Bx, respectively, where x represents the doping concentration of diols (wdiol/wSVA). After etching, the corresponding porous materials are denoted as 'eSVA/Nx', 'eSVA/Ex', and 'eSVA/Bx', respectively. For example, 'eSVA/N0' refers to pure SVA after etching, and 'eSVA/N5' refers to NPG-doped SVA with doping concentration of 5% after etching.