Carbon aerogels with 3D networks of interconnected nanometer-sized particles exhibit fascinating physical properties and show great application potential. Efficient and sustainable methods are required to produce high-performance carbon aerogels on a large scale to boost their practical applications. An economical and sustainable method is now developed for the synthesis of ultrathin carbon nanofiber (CNF) aerogels from the wood-based nanofibrillated cellulose (NFC) aerogels via a catalytic pyrolysis process, which guarantees high carbon residual and well maintenance of the nanofibrous morphology during thermal decomposition of the NFC aerogels. The wood-derived CNF aerogels exhibit excellent electrical conductivity, a large surface area, and potential as a binder-free electrode material for supercapacitors. The results suggest great promise in developing new families of carbon aerogels based on the controlled pyrolysis of economical and sustainable nanostructured precursors.