The chloroplatinic acid and nickel chloride as raw materials, ammonium chloride as pore-forming agent, are used to synthesize PtNi alloy 3D-nanoframeworks materials by spray drying method combined with calcination reduction. The PtNi alloy 3D-nanoframeworks materials can enhance catalytic oxidation performance of methanol. The influence of ammonium chloride or no chloride on the formation of PtNi alloy 3D-nanoframeworks materials was studied, and the effects of PtNi alloy 3D-nanoframeworks with different structures on the activity and stability of catalytic methanol oxidation were investigated in detail. The results showed that the PtNi alloy prepared by adding appropriate amount of ammonium chloride has a single solid solution structure (fcc), which is composed of curved nanowires interwoven to form 3D-nanoframeworks. And the diameter of the nanowires is less than 10 nm, and the nanopore is about 10 nm. Compared with commercial Pt black catalysts and PtNi alloy nanomaterials without ammonium chloride, PtNi alloy 3D-nanoframeworks materials has higher catalytic methanol oxidation activity (611.4 mA·mg-1Pt), which is 3.58 times (170.8 mA·mg-1Pt) of commercial Pt black and 1.36 times (448.8 mA·mg-1Pt) of PtNi alloy nanomaterials without ammonium chloride, respectively. The order of stability in catalytic methanol oxidation reaction is: PtNi alloy 3D-nanoframeworks materials > PtNi alloy nanomaterials without ammonium chloride >commercial Pt black catalyst. In addition, In this paper, the method is extended to successfully prepare PtNiCoCuRuIrPd high-entropy-alloy 3D-nanoframeworks materials.