A　series　of　NiMo/FDU-12　catalysts　with　tunable　pore　diameters　and　mesostructures　have　been　controllably　synthesized　by　adjusting　the　synthetic　hydrothermal　temperature　and　applied　for　the　hydrodesulfurization　of　dibenzothiophene　and　its　derivative.　The　state-of-the-art　electron　tomography　revealed　that　the　pore　sizes　of　FDU-12　supports　were　enlarged　with　the　increase　in　the　hydrothermal　temperature　and　the　mesostructures　were　transformed　from　ordered　cage-type　pores　to　locally　disordered　channels.　Meanwhile,　the　MoS2　morphology　altered　from　small　straight　bar　to　semibending　arc　to　spherical　shape　and　finally　to　larger　straight　bar　with　the　change　of　support　structures.　Among　them,　FDU-12　hydrothermally　treated　at　150 °C　possessed　appropriate　pore　diameter　and　connected　pore　structure　and　was　favorable　for　the　formation　of　highly　active　MoS2　with　curved　morphology;　thus,　its　corresponding　catalyst　exhibited　the　best　HDS　activity.　Furthermore,　it　was　indicated　that　the　isomerization　pathway　could　be　significantly　improved　for　HDS　of　4,6-dimethyldibenzothiophene　after　the　addition　of　aluminum,　which　was　expected　to　be　applied　to　the　removal　of　the　macromolecular　sulfur　compounds.　Our　study　sheds　lights　on　the　relationship　between　support　effect,　active　sites　morphology　and　HDS　performance,　and　also　provides　a　guidance　for　the　development　of　highly　active　HDS　catalysts.　©　2020,　The　Author(s).