A first example of 2D Zn2(bim)4 film with an infinite aspect ratio is demonstrated which is ideal for H2selective transport controlled by the 4-MR aperture oriented along the c-out-of-plane direction. As a result, extremely high H2/CO2 separation performance was obtained under pressurized conditions. This was achieved by extremely simple crystallization conditions (room temperature synthesis within minutes) and by improving environmental sustainability (use of water as solvent). The high performance of the film is attributed to the in-plane intergrowth of the film limiting the defective pathway. These findings will inspire the development of other promising MOF frameworks in the 2D film morphology to improve the performance for a wide range of separation processes.