An electroassisted filtration technique has been employed to improve dewatering of a suspension of micro-fibrillated cellulose (MFC) produced via 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation. In addition, all-atom molecular dynamic (MD) simulations were performed to deepen the understanding of the complicated dewatering mechanism on a molecular level. Both the experimental and the simulation results implied that the dewatering rate was not only improved when electroassisted filtration was used but also found to be proportional to the strength of the electric field. A channeled dewatered structure was observed for these experiments and may have contributed to enhanced dewatering by providing high overall permeability. The MD simulations revealed that the electric field had a significant impact on the fibril movement, whereas the impact of pressure was limited. The simulations also suggested that the increased filtrate flow upon the application of an electric field was not only due to electroosmotic flow but also due to electrophoretic movement of the fibrils toward the anode that led to the release of water that had been trapped between the fibrils, allowing it to be pressed out together with the rest of the bulk water. This study shows that electroassisted filtration has the potential to improve the dewatering of TEMPO-MFC, and the MD simulations provide further insights into the dewatering mechanism.