The present work demonstrates the spinning of conductive filaments from oppositely charged nano-scale entities, i.e., cationic cellulose nanocrystals (CNC) and anionic graphene oxide (GO), via interfacial nanoparticle complexation. Especially, the role of CNC and GO concentration in filament formation was investigated. Moreover, the chemical structure, morphology and composition of formed CNC/GO composite filaments were further characterized. The positively charged CNC formed firstly a complex film with negatively charged GO flake and then the complexed structures were further assembled into macroscale hybrid filament (diameter about 20 to 50 μm). After chemical reduction of the hybrid filament, conductive filaments with an average tensile strength of 109 ± 8 MPa and electrical conductivity of 3298 ± 167 S/m were obtained. The presented approach provides a new pathway to understand the interaction of GO and nanocellulose, and to design macroscopic, assembled and functionalized architectures of GO and nanocellulose composites.