To comprehensively develop and utilize Camellia resources, fractions of ethanol extract of Camellia semiserrata Chi. cake were separated and identified. Five purified compounds with purity of 99.2%, 95.4%, 97.5%, 99.1% and 97.4%, respectively, were achieved. By using affiliated molecular formula of generator by Agilent high-resolution mass spectrometry workstation Qualitative Analysis B.06.00, formula of MS fragmentation of molecular ions were calculated, combining with fragmentation patterns of compounds and physical and chemical properties, the compounds were identified as protocatechuic acid and four kinds of flavonoids.