The invention relates to a natural gas hydrate inhibitor, a natural gas hydrate compounding inhibitor, and preparation methods of the natural gas hydrate inhibitor and the natural gas hydrate compounding inhibitor. The preparation method of the natural gas hydrate inhibitor comprises: 1, dissolving N-vinyl caprolactam and an amide-containing monomer in deionized water to obtain a mixed solution A;2, carrying out a reaction on the mixed solution A and azobisisobutyronitrile for 4-10 h at a temperature of 50-90 DEG C, and filtering the obtained reaction solution to obtain a product; and 3, removing impurities from the product, and drying to obtain the natural gas hydrate inhibitor. The preparation method of the natural gas hydrate compounding inhibitor comprises: 1, preparing a natural gashydrate inhibitor aqueous solution with a mass fraction of not more than 5% from the natural gas hydrate inhibitor; and 2, adding a thermodynamic inhibitor to the aqueous solution according to a massratio of the thermodynamic inhibitor to the water of less than or equal to 5% to obtain the natural gas hydrate compounding inhibitor. According to the present invention, the inhibitor can significantly improve the inhibitory performance on natural gas hydrates, and the compounding inhibitor can enhance the inhibitory performance of hydrate inhibitors so as to achieve good inhibitory effect at a high under-cooling-degree.