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This invention discloses a method for preparing pentaerythritol oleate based on sodium bisulfite. The method involves the esterification reaction of pentaerythritol and oleic acid with sodium bisulfite as an auxiliary agent. Sodium bisulfite, as an auxiliary agent, possesses both catalytic and antioxidant functions, effectively improving the reaction rate and product yield while suppressing oxidation side reactions. This eliminates the need for additional antioxidants, improving product quality and reducing costs. The preparation method is simple, mild, and environmentally friendly, with readily available raw materials, low-cost auxiliary agents, and easy separation. After the reaction, the catalyst is removed by hot filtration, and unreacted oleic acid is removed by solvent extraction, effectively reducing the product's acid value. The extracted potassium oleate byproduct has a purity of 80%–90% and can be used as a flotation agent, release agent, or raw material for lubricant production, making it suitable for industrial applications. The resulting pentaerythritol oil is suitable for high-end lubricants, bio-based plasticizers, and environmentally friendly coatings.