Metal-organic frameworks (MOFs) which offer a variety of topologies, porous networks and high surface areas are promising and have potential for the applications of specific adsorption, isomerization, catalysis and separation. UIO-66 is the first MOF that has been observed to have reverse shape selectivity. However, such reverse shape selectivity of MOFs has never been explored for capillary gas chromatographic separation. Here we report the fabrication of MOF UIO-66 coated capillary column and exploration of the reverse shape selectivity and molecular sieving effect of such column for capillary gas chromatographic separation of alkane isomers and benzene homologues with excellent selectivity and precision. The adsorption enthalpies and entropies on the interaction between hydrocarbons and UIO-66 were measured to illustrate the energy effect on the separation of alkane isomers and benzene homologues on the UIO-66 coated capillary column. UIO-66 coated capillary column gave preferential retention of branched alkane isomers over their linear isomer, showing reverse shape selectivity, making UIO-66 coated capillary column attractive for capillary gas chromatographic separation of alkane isomers. iso-Propylbenzene (branched) eluted after n-propylbenzene on the UIO-66 coated capillary column again shows reverse shape selectivity. However, much bulkier 1,3,5-trimethylbenzene eluted earlier than n-propylbenzene and iso-propylbenzene on the UIO-66 coated capillary column, exhibiting molecular sieving effect. The combination of reverse shape selectivity with molecular sieving effect makes the UIO-66 coated capillary column promising for the separation of structural isomers.