A unique core/shell structured inverse opal (IO) TiO2/PANI hybrid is fabricated. The 3D inverse opal (IO) structure of TiO2 gives interconnected macropores. The hybrid electrode gives a large specific capacity of 196.59 mA h g−1 at 5 mVs−1. Symmetric cell is successfully fabricated using the IO TiO2/PANI hybrid electrode.