Here, the phase behaviors of polystyrene-block-poly(L-lactide) (PS-PLLA) diblock copolymers are studied, and network phases can be found. In addition to conventional double gyroid phase with double networks, a single network phase (an Fddd phase with orthorhombic network) can be found, as evidenced by small-angle X-ray scattering and transmission electron microscopy (TEM). The single network texture with trivalent connectors of the Fddd can be directly visualized by using 3D TEM (i.e., electron tomography), and the observation under polarized light microscopy shows its birefringence character. The formation of stable Fddd is attributed to intrinsic inhomogeneity in the chain conformations of the chiral block (i.e., PLLA). Subsequently, nanoporous PS with continuous nanochannel networks can be obtained by hydrolysis of the PLLA block in the PS-PLLA and then used as a template for sol-gel reaction of tetraethyl orthosilicate. Consequently, nanoporous SiO2 with free-standing, well-defined network texture can be fabricated after removal of the PS template to give an open-cell porous ceramic material with high specific surface area (as high as 1170 m(2)/g) due to its nanostructured texture and high porosity.