The effect of the introduction of ZnO into the NiMoW/Al2O3 hydrotreating catalyst on its activity in dibenzothiophene (DBT) hydrogenolysis has been studied. To select the optimal method for introducing the modifier, a series of samples has been prepared with ZnO added at different stages of the catalyst synthesis. Before the test, the catalysts were sulfided. The catalysts have been tested in the dibenzothiophene hydrogenolysis reaction was under hydrogen pressure using a continuous-flow microreactor. The interrelation of the active phase morphology, as well as the route of addition and amount of the added modifier with the catalytic activity of the samples has been revealed. Modification of the support by adding ZnO in an amount of 0.5 wt % increases the activity of the catalyst in DBT hydrogenolysis.