Camellia japonica L. (Theaceae) is an evergreen shrub, which is cultivated as a popular ornamental tree in Korea, China, and Japan and its seeds have been used as a source of cooking oil, in cosmetic uses and as a traditional medicine in Asia. Intensive phytochemical works have revealed that oleanane-type saponins are the characteristic compounds of the seeds of C. japonica. The purpose of the present study is to isolate and determine oleanane-type saponins from C. japonica using high-performance countercurrent chromatography (HPCCC) coupled with reversed-phase high-performance liquid chromatography (RP-HPLC) and spectroscopic evidences, respectively. HPLC-ESI-Q-TOF-MS observed a variety of saponins with di-, tri-, tetra-saccharides as oligo-glycoside moieties from the enriched saponin extract of Camellia japonica seeds. HPCCC and RP-HPLC methods were applied to give nine undescribed saponins, camoreosides A-I. The structures were determined utilizing ESI-Q-TOF-MS, 1D-, 2D-NMR, and optical rotation. This result indicates that combination HPLC-ESI-Q-TOF-MS analysis and HPCCC coupled with RP-HPLC are excellent tools for discovering novel saponins from natural sources.