Pu-er ripe tea is a special microbial post-fermented tea made from Pu-er raw tea, a kind of green tea produced from the leaves of Camellia sinensis var. assamica. It is one of the most consumed teas in the past two decades in China, due to its special flavor, taste, and beneficial effects. This work aimed to obtain diverse catechin structures from Pu-er ripe tea, which led to the isolation of four new phenylpropanoid-substituted flavan-3-ols, puerins C-F (1-4), together with four known fiavan-3-ols, (+)-catechin (5), (-)-epicatechin (6), (+/-)-gallocatechin (7), and (-)-epigallocatechin (8). Their structures were elucidated on the basis of detailed spectroscopic analysis, including ID and 2D NMR mass and CD spectra. Compounds 1-4, which could be formed in the post-fermentative process of Pu-er tea, were isolated for the first time from tea and Theaceae plant.