Herein, we report a direct synthesis route for 2D Zn2(bim)4 film with an infinite aspect ratio. This is achieved at room temperature, in an aqueous precursor solution, in a rapid fashion (a few minutes), making the process simple. Ultrathin, oriented film down to 4 nm in thickness could be achieved. 4-MR apertures in 2D Zn2(bim)4 films are oriented perpendicular to the transport direction. The resulting membranes outperform the state-of-the-art membranes under pressurized high-temperature feed conditions.