A high-efficiency electro-thermal heater requires simultaneously high electrical and thermal conductivities to generate and dissipate Joule heat efficiently. A low input voltage is essential to ensure the heater’s safe applications. However, the low voltage generally leads to low saturated temperature and heating rate and hence a low thermal efficiency. How to reduce the input voltage while maintaining a high electro-thermal efficiency is still a challenge. Herein, a highly electrical and thermal conductive film was constructed using a graphene-based composite which has an internal three-dimensional (3D) conductive network. In the 3D framework, cellulose nanocrystalline (CNC) phase with chiral liquid crystal manner presents in the form of aligned helix between the graphene oxide (GO) layers. Carbon nanodots (CDs) are assembled inside the composite as conductive nanofillers. Subsequent annealing and compression results in the formation of the assembled GO-CNC-CDs film. The carbonized CNC nanorods (CNR) with the helical alignment act as in-plane and through-plane connections of neighboring reduced GO (rGO) nanosheets, forming a conductive network in the composite film. The CDs with ultrafast electrons transfer rates provide additional electrons and phonons transport paths for the composite. As a result, the obtained graphene-based composite film (rGO-CNR-CDs) exhibited a high thermal conductivity of 1,978.6 W·m−1·K−1 and electrical conductivity of 2,053.4 S·cm−1, respectively. The composite film showed an outstanding electro-thermal heating efficiency with the saturated temperature of 315 °C and maximum heating rate of 44.9 °C·s−1 at a very low input voltage of 10 V. The freestanding graphene composite film with the delicate nanostructure design has a great potential to be integrated into electro-thermal devices.