Free-standing nanocellulose/ZIF-67 derived porous Co3O4 polyhedron hybrid dual-layer films were layer-by-layer successfully assembled by a water-based paper-making process. Nanocellulose (NFC) not only served as flexible substrate, but also it substituted expensive polymer binders to reduce the cost in the dual-hybrid film electrodes. Besides, the NFC/porous Co3O4 polyhedron composite (NPC) layer replaced the traditional metal current collector to be a free-standing electrode. The flexible NPC-60 film electrode (the ratio of porous Co3O4 polyhedron to NFC component was 60:30) had a higher capacitance (594.8 mF cm−2 at 5 mV s−1 in 6 M KOH) than other samples, and a power density of 799.97 W·kg−1 at the energy density of 18.75 Wh·kg−1. With the increase of NFC content, the hybrid film can be bent and rolled demonstrating that the hybrid film has good flexibility and foldability. This work provides an insight perspective for metal organic framework (MOF)-derived metal oxide powders to form flexible and free-standing supercapacitor electrodes.