Metal-organic frameworks (MOFs) have been at the forefront of research activity for almost two decades now. In the present work, we developed various MOFs that can carry out many energy-intensive separations either by a periodic arrangement of requisite functionalities in the channels for optimal host-guest interactions or by tuning the aperture size of the channel window to afford size-selective separations. We were able to achieve many industrially important separations like CO2 capture, olefin/paraffin separation, branched/linear paraffin separation and natural gas upgrading. Molecular-level Insight was obtained for a better understanding of the separation processes. In collaboration with industrial partners, some of the MOFs with exceptional performance will be investigated in a real like conditions at demonstration scale for taking them to the next level. Economical and rapid scale-up methods for these materials are being developed and we have successfully produced these materials in kg quantities.