Superacidic catalyst systems based on sulfated zirconia, mixed heteropoly acids, and nano-sized nickel powder applied on acid-activated montmorillonite are proposed. The mechanisms of the propane-propylene fraction oligomerization process on superacidic catalysts are studied in a wide range of temperatures, pressures, and volumetric feedstock feed rates. It is shown that catalysts with a degree of montmorillonite modification with 2.5% nano-sized nickel, which exhibit the best activity and propylene trimer selectivity, are the most promising from the viewpoint of introduction of the oligomerization process at oil-processing/refining enterprises.