The electrocatalytic oxygen evolution reaction (OER) is a highly important reaction that requires a relatively high overpotential and determines the rate of water splitting—a process for producing hydrogen. The overall OER performance is often largely limited by uncontrollable interface when active catalysts are loaded on conductive supports, for which polymer binders are widely used, but inevitably block species transportation channels. Here, a scalable fabrication approach to freestanding graphitized carbon nanofiber networks is reported, which provides abundant sites for in situ growing Fe/Ni catalysts with the improved interface. The fabricated hybrid membrane exhibits high activity and durability toward OER, with an overpotential of 280 mV at a geometrical current density of 10 mA cm−2 and a Tafel slope of 30 mV dec−1 in alkaline medium. As implemented as a freestanding electrode, the 3D hybrid structure achieves further enhanced OER performance with an overpotential down to 215 mV at 10 mA cm−2. This work provides fresh insights into rationally fabricating OER electrocatalysts from the angle of electrode design.