The invention particularly relates to a nano wall structure composed of flaky tin oxide and a preparation method thereof. The method takes a stannous oxide powder and carbon powder mixture as a source material, and utilizes a thermal evaporation method for growing. The edge of the prepared nano wall structure is irregular, the side face of each wall is not smooth, the diameter is about 100-1000 nm, and the thickness is about 30 nm. The nano wall structure can be grown on a silicon slice substrate in a large area; with the characteristics of unique structure, oxidation resistance, high-temperature resistance, high field emission current density, lower turn-on field, effective avoiding of a field shielding effect, good emission stability and the like, an application of the nano wall structure in a field emission device can be achieved; and the structure has large specific surface area, can obviously enhance sensitive properties of a tin oxide material on various chemical gases, can be used as a gas sensitized material applied in the micro/nano sensor field, thereby having great scientific research values and wide commercial application prospects.