Pd　nanoparticles　(∼2.1　nm)　supported　on　biomolecule-derived　graphene-like　carbons　have　been　studied　as　highly　active　and　stable　catalysts　for　the　selective　hydrogenation　of　quinolines.　A　novel　strategy　is　developed　by　pyrolysis　of　guanine　with　H2SO4,　yielding　heteroatom-doped　(N/O,　N/O/S)　and　minimally　layered　carbon　nanosheets　with　large　accessible　areas,　which　can　facilitate　mass　transfer　and　stabilize　Pd　nanoparticles.　XPS　results　indicate　that　the　intensity　ratio　of　Pd0/Pd2+　increases　with　N/S　codoping　in　graphene-like　carbons,　suggesting　a　significant　correlation　between　support　properties　and　electronic　structure　of　Pd　species.　N/O/S-codoped　Pd@GS1000　shows　substantially　enhanced　activity　for　quinoline　hydrogenation　reactions,　with　almost　＞99%　conversion　and　＞99%　selectivity　to　1,2,3,4-tetrahydroquinoline　under　mild　catalytic　conditions,　superior　to　Pd@G1000　(without　sulfur　doping)　and　the　reference　Pd/OCNT　catalyst.　Further　investigation　indicates　that　sulfur-containing　carbon　nanosheets　strongly　interact　with　metal　supports,　and　thus　metallic　Pd　can　be　regarded　as　an　active　center　for　hydrogenation　reactions.　This　work　may　provide　a　framework　for　the　development　of　promising　applications　of　supported　catalysts　based　on　ultrathin　carbon　nanosheets　in　fine　chemical　production.　©　2019　American　Chemical　Society.