Polyvinylferrocene (PVF) has rarely been used for energy storage despite its stable one-electron redox electrochemistry, flat charge/discharge profile, and high coulumbic efficiency. This is due to its low intrinsic conductivity and the compromise between the electronic/ionic conductivity and the redox center utilization efficiency of PVF. In this work, we overcome this limitation by simultaneous electro-polymerization of pyrrole and electro-precipitation of PVF on the electrode surfaces. Due to the intermolecular interactions between pyrrole and the ferrocene moieties of PVF, the as-polymerized conducting PPy becomes intertwined with the poorly conducting PVF, forming a highly porous polymer hybrid with facilitated electron transport and ionic diffusion. A total specific capacitance of 514.1 F/g was realized for the PVF/PPy hybrid as a result of the synergistic effects between the constituent polymers.