The invention relates to a method for extracting high-purity caffeine from tea leaves and belongs to the technical field of extraction. By-product caffeine crude products obtained during production of tea polyphenols are utilized, caffeine is crystallized in water, the method is safe and free of toxicity, cost is reduced, and both the value and the income are increased. The method is easy to operate and environmentally friendly, the energy consumption of the film separation technology is low, selectivity is high, and a device is flexible; a column chromatography method is simple in operation technology, high in efficiency and good in safety; due to the method that the film separation technology is combined with column chromatography, tea polysaccharide, tea polyphenols, theanine and other components are effectively separated, and subsequent crystallization and purification of caffeine are facilitated; re-crystallization is performed through water, and the method is safe, free of toxicity, environmentally friendly, high in yield and low in cost; the method has the advantages that energy consumption is low in the freezing and crystallizing process, no solvents residuals exist, and product purity is high, the method is simple, both the value and the income are increased, and the method has wide application prospects.