The rational design of artificial solid‐state nanopores is of great importance in the discovery of intriguing ion transport phenomena. 2D metal–organicframework (2D MOF) nanosheets with single crystallinity, aligned nanochannels, ultrathin thickness, and diverse functionalities are highly potential solid‐state nanopores. An electrophoretic method is developed to successfully fabricate MOF nanopores supported by SiNx substrate, which is confirmed by high‐resolution transmission electron microscopy. A giant gap around 4 V together with ionic current rectification is discovered in nonlinear voltage‐activated current‐voltage curves, revealing the synergy of the hydrophobic effect and charge effect in MOF nanopores. The charge effect embodies the different contribution current which results from the enrichment and depletion of ions in MOF nanopores by COMSOL simulation. Moreover, 2D MOF nanosheets with different surface charges, hydrophobicity, and pore sizes demonstrate the universality of nanopore fabrication and further confirm the synergistic mechanism. The nonlinear ion transport in the ultrathin MOF nanosheets will provide an opportunity to explore further applications in solid‐state nanopores. Nonlinear ion transport through the single crystalline two‐dimensional ultrathin metal–organic framework nanosheets is discovered along with a giant gap of low conductance state as well as the rectification inversion. The synergetic mechanism is revealed by the combination of the regulation of physical and chemical parameters and simulations.