Dimethoxymethane　(DMM)　has　wide　application　in　resin,　solvent,　and　fuel　fields　as　a　fundamental　organic　chemical.　The　traditional　route　to　synthesize　DMM　using　methanol　and　formaldehyde　as　reactants　via　condensation　reaction　has　poor　efficiency.　Methyl　nitrite　(MN),　which　is　obtained　by　the　reaction　of　methanol,　oxygen　and　nitrite　monoxide　without　catalysts,　could　be　used　as　raw　material　to　produce　DMM　through　catalytic　decomposition.　The　current　work　systematically　investigated　the　catalytic　activity　and　selectivity　to　DMM　of　several　molecular　sieves　in　MN　decomposition　reaction.　The　results　show　that　the　activity　trend　is　NaY　(97%)=HY　(97%)＞　HZSM-5　(90%)＞H　beta　(89%)＞NaZSM-5　(18%)＞Na　beta　(6%),　and　the　DMM　selectivity　trend　is　NaY　(53%)＞HY　(12%)=Na　beta　(12%)＞NaZSM-5　(7%)＞H　beta　(4%)＞HZSM-5　(3%).　X-ray　diffraction　(XRD),　Brunner-Emmet-Teller　measurements　(BET),　scanning　electron　microscope　(SEM)　and　Pyridine-IR　(Py-IR)　experiments　have　been　employed　to　reveal　the　structure-activity　relationship　of　these　molecular　sieves.　Combining　the　temperature-programmed　desorption　of　CO2　experiments　(CO2-TPD)　data　with　the　evaluation　results　of　the　catalytic　performance　of　the　zeolite　catalyst,　the　basic　sites　of　the　zeolite　have　no　direct　connection　to　the　catalytic　MN　decomposition　process.　Meanwhile,　the　calcination　temperature　experiment　of　NH4-zeolite　and　the　catalytic　performance　test　experiment　of　NaY-tetraethoxysilane　(TEOS)　further　proved　that　the　acid　site　played　an　essential　role　in　promoting　the　decomposition　of　MN,　and　the　results　show　that　the　Lewis　acidity　sites　of　Na+　and　low-coordinated　Al　metal　center　are　key　factors　to　catalyze　MN　to　DMM　high　selectively.　We　have　proposed　the　MN　decomposition　mechanism.　In　the　process　of　MN　decomposition,　there　are　both　proton　generation　and　proton　consumption　processes.　Intermediates　in　the　decomposition　process　are　easily　protonated　by　Bronsted　acid　sites　to　form　by-products.　The　Lewis　acid　site　of　zeolite　is　generally　a　low-coordinated　Al　metal　center,　which　can　effectively　adsorb　and　stabilize　the　oxygen-containing　intermediates　generated　during　the　decomposition　of　MN,　especially　the　methoxy　and　formaldehyde　intermediates　involved　in　the　production　of　DMM,　which　is　very　beneficial　to　the　decomposition　of　MN　to　DMM.　We　believe　that　the　research　in　this　paper　can　provide　a　new　and　efficient　synthetic　route　for　DMM.