Molybdenum and rhenium selenides hierarchical structures consisting of self-assembled few-layered stacked nanosheets were synthesized via a solvothermal route, by reacting rhenium and molybdenum carbonyls, selenium powder, and p-xylene as solvent. Both materials were evaluated and compared in the hydrodesulfurization (HDS) of dibenzothiophene (DBT). The characterization techniques revealed dif-ferent morphologies for both diselenides: MoSe2 has a flowerlike microstructure composed of few-layered stacked nanosheets, while ReSe2 shows a microspherical structure with smaller and randomly oriented few-layered stacked nanosheets. The HDS catalytic activity displayed by ReSe2 was more than twice than that obtained for MoSe2, with a clear preference for the direct desulfurization (DDS) path. (C) 2021 Elsevier B.V. All rights reserved.