The transformation of 2,5-dimethyl-hexadiene-2,4 and benzothiophene over mesoporous MCM-41 silica supported Ni-Mo sulfide catalyst was estimated. The physico-chemical properties of support and catalyst were evaluated by XRD, low-temperature N2 adsorption, TEM, EDX mapping and XPS analysis. The catalyst reveals the sulfide particles with 5.4 nm in length and 3.5 stacks supported on MCM-41 silica having hexagonal porous arrangement with 2.5 nm in diameter. The effective content of Mo in MoS2 was 48.3 wt%. According to thermodynamic calculations, the equilibrium mixture contains 2,5-dimethylhexane (82 %) and n-octane (18 %). For catalytic tests, at 260–340 °C for 1–2 h selectivity to olefins reaches 85–90 %, whereas 100 % benzothiophene conversion to ethylbenzene was achieved at 300–340 °C for 6–10 h. n-Octane was detected as the product of skeletal isomerization of 2,5-dimethyl-hexadiene-1,5. For model FCC gasoline, the optimal conditions providing effective sulfur removal and selective hydrogenation were defined as 300–320 °C and 2–4 h under 3–5 MPa hydrogen pressure. The reusability of the catalyst was evaluated using model feed containing BT and C8H14 with molar ratio of 2:1 under 5 MPa hydrogen pressure at 320 °C for 2 h without any pre-treatment or regeneration of the catalyst before the next reaction run. In was established that HDS/HYDO selectivity increases with reaction run, which is due to the conversion of C8H14 decrease more significant as compared to that for BT, whereas conversion and product distribution maintain unchanged from 5 reaction run, indicating that the catalyst is running-in. For the spent NiMoS/MCM-41 catalyst the effective content of Mo in MoS2 phase reaches 42.8 wt%, whereas that for Ni in NiS and NiMoS phase was 1.7 wt% and 0.7 wt%, respectively, which is compared to those values for the fresh sample.