Imparting electro-conductive properties to nanocellulose-based products may render them suitable for applications in electronics, optoelectronics, and energy storage devices. In the present work, an electro-conductive nanocrystalline cellulose (NCC) film filled with TiO₂-reduced-graphene oxide (TiO₂-RGO) was developed. Initially, graphene oxide (GO) was prepared using the modified Hummers method and thereafter photocatalytically reduced using TiO₂ as a catalyst. Subsequently, an electro-conductive NCC film was prepared via vacuum filtration with the as-prepared TiO₂-RGO nanocomposite as a functional filler. The TiO₂-RGO nanocomposite and the NCC/TiO₂-RGO film were systematically characterized. The results showed that the obtained TiO₂-RGO nanocomposite exhibited reduced oxygen-containing group content and enhanced electro-conductivity as compared with those of GO. Moreover, the NCC film filled with TiO₂-RGO nanocomposite displayed an electro-conductivity of up to 9.3 S/m and improved mechanical properties compared with that of the control. This work could provide a route for producing electro-conductive NCC films, which may hold significant potential as transparent flexible substrates for future electronic device applications.