We suggest an efficient and simple synthetic strategy to prepare interconnected hierarchically porous anatase TiO2 (IHP-A-TiO2) nanofibers by two synergetic effects: phase separation between polymers and relative humidity control during electrospinning. The macro channels formed by polystyrene decomposition were interconnected by numerous mesopores that were formed by evaporation of infiltrated water vapor in the structure. The resulting IHP-A-TiO2 nanofibers showed better Li+ ion storage performances than the TiO2 materials reported in the literature. The discharge capacity of IHP-A-TiO2 nanofibers for the 3000th cycle at 1.0 A g-1 and corresponding coulombic efficiency from the 20th cycle onward were 142 mA h g-1 and >99.0%, respectively. Well-interconnected, ultrafine TiO2 nanocrystals within the nanofiber showed structural stability during cycling and facilitated facile charge transfer at the electrode-electrolyte interface.