By coupling the self-assembly of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) containing titanium precursors with the electrospinning technique, novel cigarlike nanofibers with an outer-shell and inner-continuous-pore structure and resultant fabrics were fabricated. Different from typical porous metal oxides, the prepared high-surface-area nonwoven fabrics show excellent mechanical properties. Not only are these fabrics self-supporting over a large area, but they can also be cut using scissors, which is important for large-scale applications. Furthermore, as electrode materials in Li-ion batteries, these fabrics exhibit much higher charge/discharge capacity and cycle stability compared with the commercially available nanosized TiO2 (P25). The improved mechanical and electrochemical performances are attributed to the presence of an outer-shell, inner-bicontinuous structures (including continuous TiO2 frame and continuous nanopores) and hierarchical pores from the cigarlike nanofibers.