A series of samples with varying cross-linking degree were prepared from the same 1,2-polybutadiene-b-polydimethylsiloxane (1,2-PB-b-PDMS) diblock copolymer precursor. The stability of nanopores generated after PDMS cleaving depends on the cross-linking degree of 1,2-PB. The swelling ratio of the cross-linked samples in toluene was converted into a degree of cross-linking following the Flory scheme; a simple relation between the Flory cross-linking degree and the fraction of consumed double bonds during the cross-linking reaction followed. The structure of the block copolymer at different stages of preparation was characterized by small-angle X-ray scattering (SAXS). In addition, scanning electron microscopy (SEM) gave direct images of the nanoporous polymer structure. Nanocavities are accessible to methanol, and observations of methanol uptake were combined with structural information from SAXS. This permits a classification of the bulk cross-linked and etched polymers into three groups: collapsed, traced, and nanoporous materials.