Solid-state NMR spectroscopy in conjunction with theoretical calculation was employed to investigate the adsorbent–adsorbate host–guest interactions during propane/propylene separation on ZIF-8. ¹H NMR chemical shifts of free gaseous and adsorbed propane/propylene are unambiguously assigned with the assistance of two-dimensional (2D) ¹H-¹H correlation spectroscopy (COSY) MAS NMR spectra. Meanwhile, the adsorption selectivity for propane/propylene mixtures on ZIF-8 at a pressure in range of 1.9–9.6 bar is quantitatively determined using ¹H MAS NMR experiments, which agreed well with the ideal adsorbed solution theory (IAST) predictions. The preferential adsorption of propane compared with propylene on ZIF-8 is directly visualized from the 2D ¹H-¹H spin diffusion homo-nuclear correlation (HOMCOR) MAS NMR spectroscopy. Moreover, the preferential adsorption sites for propane and propylene are deduced from the ¹H-¹H spin diffusion buildup curves, which is further confirmed by DFT theoretical calculations. This work provides insights to understand the structure–property relationship during the propane/propylene separation on ZIF-8 as adsorbent.