Separation of paraffin isomers is of great importance in the refining industry because of their potential applications for energy efficiency, as reflected by their associated Research Octane Number (RON) values. Here, we report the synthesis of the first zeolite-like metal–organic framework (ZMOF) with ana topology that displays helicoidally/cylindrically-shaped channels with a pore-aperture size of ca. 3.8 × 6.2 Å. Markedly, such structural features offer potential for the selective separation of linear, and mono- and dibranched paraffins. Largely due to its tuned pore size and the presence of ions in the channels, ana-ZMOF possesses an excellent uniform charge density that allows the kinetic separation of n-pentane versus iso-pentane and n-butane vs. iso-butane, as well as the molecular exclusion of 2,2,4-trimethyl pentane.