Efficient enhancement of catalytic stability and coke-resistance is a crucial aspect for dry reforming of methane. Here, we report Ni nanoparticles embedded on vacancy defects of hexagonal boron nitride nanosheets (Ni/h-BNNS) can optimize catalytic performance by taming two-dimensional (2D) interfacial electronic effects. Experimental results and density functional theory calculations indicate that surface engineering on defects of Ni/h-BNNS catalyst can strongly influence metal-support interaction via electron donor/acceptor mechanisms and favor the adsorption and catalytic activation of CH4 and CO2. The Ni/h-BNNS catalyst exhibits superior catalytic performance during a 120 h durability test. Furthermore, in situ techniques further reveal possible recovery mechanism of the active Ni sites, identifying the enhanced catalytic activities of the Ni/h-BNNS catalyst. This work highlights promotional mechanism of defect-modified interface and should be equally applicable for design of thermochemically stable catalysts.