The　adsorption　behavior　of　methyl　nitrite　(MN)　on　the　closed-packed　Pd(111)　surface　has　been　investigated　in　detail　by　using　density　functional　theory　(DFT).　MN　binds　to　the　surface　in　two　alternative　forms,　using　the　nitrogen　atom　attached　to　the　surface.　An　overall　net　charge　transfer　from　the　substrate　to　the　cis-MN　molecule　is　also　confirmed.　In　addition,　the　reaction　mechanism　for　the　dissociation　of　MN　on　the　Pd(111)　surface　has　been　identified　and　compared　with　the　methanol　decomposition　via　O-H　scission.　The　results　demonstrate　that　MN　is　a　more　active　reactant　than　methanol　for　the　oxidative　addition　to　the　Pd　catalyst.　The　possible　reason　has　been　analyzed　from　the　adsorption　behaviors　and　reaction　barriers,　that　is,　MN　is　chemically　absorbed　on　the　Pd(111)　surface;　the　CH3O-NO　bond　scission,　leading　to　the　formation　of　adsorbed　methoxy　species,　is　much　more　favorable　than　that　of　the　O-H　bond　scission　and　has　a　large　exothermic　behavior.