In　alumina-based　catalysts　the　properties　of　the　alumina　support　directly　influence　the　structure　(size,　morphology,　orientation,　etc.)　of　the　resulting　active　phase　and　ultimately　determine　the　performance　of　the　final　catalysts.　This　paper　presents　a　facile　and　efficient　method　for　gamma-Al2O3　to　simultaneously　expose　a　{111}　facets　with　strong　acidity　and　{110}　facets　with　moderate　basicity.　It　is　shown　that　the　metal　oxides　NiOx　and　MoOx　can　be　selectively　deposited　and　subsequently　sulfided　on　the　respective　facets　to　form　a　NiS2-MoS2/Al2O3　catalyst　with　substantially　enhanced　activity　for　thio-etherification　reaction.　By　cooperative　action　of　the　active　sites　on　the　newly　exposed　facets,　the　catalyst　is　shown　to　have　superior　activity　over　a　conventional　NiMoS/Al2O3　catalyst　in　the　thio-etherification　reaction　between　ethanethiol　and　isoamylene　(2-methyl-2-butene)　to　yield　ethylamyl　thioethers.　Our　findings　show　that　tuning　the　physicochemical　properties　via　crystal　facet　engineering　and　inducing　cooperative　catalysis　via　preferential　deposition　of　active　metals　open　a　novel　avenue　for　the　rational　design　and　synthesis　of　high　performance　catalysts.