Palladium-based　catalysts　have　been　intensively　investigated　for　the　hydrogenation　of　nitroarenes　due　to　their　high　activity.　However,　it　remains　a　challenge　to　achieve　high　selectivity　when　reducing　or　halo　groups　are　present.　Herein,　we　propose　a　facet　engineering　strategy　to　regulate　the　activity　and　selectivity　of　Pd/TiO2　and　a　series　of　Pd/TiO2　catalysts　with　adjustable　proportions　of　(101)　and　(001)　facet　of　TiO2　were　synthesized　for　the　selective　hydrogenation　of　nitroarenes.　With　increased　percentage　of　(101)　facet,　better　dispersed　Pd　species　and　more　oxygen　vacancies　(OV)　can　be　generated　on　the　Pd/TiO2　catalyst,　thereby　providing　increasing　hydrogenation　reaction　centers　with　strongly　adsorbed　nitro　groups.　As　a　result,　the　Pd/TiO2　with　dominant　(101)　facet　and　0.1　wt%　of　Pd　loading　(Pd/TiO2-c)　delivers　an　outstanding　conversion　(100　%)　of　m-chloronitrobenzene,　high　selectivity　(96.8　%)　toward　m-chloroaniline,　and　excellent　reusability.　In　situ　characterizations　and　density　functional　theory　(DFT)　simulation　reveal　that　the　Pd/TiO2-c　exhibits　much　stronger　adsorption　toward　nitro　groups　than　chlorine　group,　while　the　catalyst　with　more　(001)　facet　shows　similar　adsorption　capability　toward　these　two　groups.　Thereby,　nitro　group　is　more　preferentially　adsorbed　and　hydrogenated　during　the　reaction　on　Pd/TiO2-c,　which　explains　the　excellent　selectivity.　Remarkably,　Pd/TiO2-c　can　also　realize　excellent　conversion　(100　%)　and　selectivity　(＞　96　%)　toward　other　functional　nitroarenes　containing　−F,　–OH,　–CHO,　–COCH2-　groups.　This　work　highlights　the　facet　engineering　of　supports　to　tune　the　physicochemical　properties　of　loaded　active　metal　and　the　adsorption　behavior　of　reactants,　and　provides　an　effective　strategy　for　the　further　development　of　efficient　Pd-based　catalysts　for　selective　nitroarenes　hydrogenation.　©　2024