To comprehensively develop and utilize Camellia semiserrata resources, compounds of ethanol extract of Camellia semise-rrata Chi. cake were separated and identified. Five purified compounds were achieved by HPLC preparation from 4 fractions including XVII, XXVI, XXVIII and XXXIV by ethyl acetate extraction and silica gel column chromatography. The analysis of compound 4 has been reported in another paper. Four compounds were identified as protocatechoic acid (1), apigenin-6-C-β-D-glucopyranoside (2), kaempferol-3-O-\[α-L-rhamnopyranosyl-(1-3)-2,4-di-O-acetyl-α-L-rhamnopyranosyl-(1-6)\]-β-D-glucopyranoside (3), and kaempferol-3-O-\[α-L-rhamnopyranosyl-(1-3)-2,4-di-O-acetyl-α-L-rhamnopyranosyl-(1-6)\]-β-D-glucopyranoside (5) by spectral analysis, among which, compounds 3 was the first time reported in the Camellia genus, and compounds 5 was firstly reported in Camellia semiserrata Chi., The structures were analyzed in detail for compounds 2 and 5, which were isolated from Camellia semiserrata Chi. for the first time, and compound 3 extracted from the camellia genus for the first time. For these three compounds ¹H and ¹³C chemical shifts were fully affiliated.