Thermal　reduction　of　CO2　by　green　H2　is　one　of　the　most　effective　strategies　for　CO2　utilization　and　preparation　of　value-added　C1　chemicals,　which　is　highly　dependent　on　the　catalyst　compositions　and　structures.　In　this　work,　hollow　mesoporous　nickel　phyllosilicate　(mNiSiO3)　with　an　average　size　of　250　nm　was　used　as　catalysts　for　CO2　hydrogenation　after　the　partial　extraction　of　Ni　ions　from　nickel　phyllosilicate.　After　the　reduction　treatment　by　H2　at　400　°C,　the　mNiSiO3-R400　showed　CO2　conversion　of　22.9%　and　CH4　selectivity　of　80.9%　(300　°C,　0.1　MPa).　Interestingly,　by　functionalization　of　two-dimensional　graphene　oxide　(GO)　onto　the　nickel　phyllosilicate　to　obtain　mNiSiO3/GO　catalyst,　more　CO　product　was　obtained　and　the　CO/CH4　ratio　in　the　products　can　be　easily　tuned　via　the　change　of　GO　loading　amount.　It　was　found　that　the　functionalization　of　GO　nanosheets　on　mNiSiO3　would　affect　the　reduction　degree　of　nickel　phyllosilicate　and　stabilize　the　structure　against　collapse　during　high-temperature　reduction.　In　accordance,　the　diffuse　reflectance　infrared　Fourier　transform　spectroscopy　(DRIFTS)　in　different　transient　states　suggested　that　the　formation　of　bidentate　carbonate　species　may　play　a　vital　role　in　the　high　selectivity　of　CO　and　that　CH3O*　was　the　key　intermediate　species　over　the　Ni　site　for　CH4　formation.　Due　to　the　electronic　interaction　between　GO　and　Ni0,　it　might　weaken　the　interaction　between　Ni0　and　H2,　which　prevents　the　direct　decomposition　of　CO*　into　C*　and　the　further　hydrogenation　of　C*　into　methane　over　the　Ni0　sites.　This　work　will　provide　new　references　for　adjusting　the　CO/CH4　selectivity　in　CO2　hydrogenation　over　the　Ni-based　catalysts.　©　2022　Elsevier　B.V.