Litchi (Litchi chinensis Sonn.) is widely accepted as a delicious fruit in China and its seeds have been commonly used in traditional Chinese medicine to relieve neuralgic pain. In the present study, chemical investigation of the 95% ethanol extract of Litchi chinensis seeds led to the isolation of four new compounds, 2α,3α-epoxy-5,7,3′,4′-tetrahydroxyflavan-(4β-8-catechin) (5), 2β,3β-epoxy-5,7,3′,4′-tetrahydroxyflavan-(4α-8-epicatechin) (7), litchiol A (9) and litchiol B (12), together with 11 known ones, 2,5-dihydroxy-hexanoic acid (1), soscopoletin (2), coumaric acid (3), protocatechuic acid (4), 2α,3α-epoxy-5,7,3′,4′-tetrahydroxyflavan-(4β−8)-epicatechin (6), pterodontriol d-6-O-β-d-glucopyranoside (8), Narirutin (10), naringin (11), dihydrocharcone-4′-O-β-d-glucopyranoside (13), pinocembrin-7-rutinoside (14), pinocembrin-7-neohesperidoside (15). Their structures were mainly elucidated on the basis of NMR, MS, IR, CD and UV spectral evidences. Antioxidant activities of 14 compounds were determined by DPPH radical-scavenging assay and Trolox equivalent antioxidant capacity assay, and the results showed that four compounds, protocatechuic acid (4), 2α,3α-epoxy-5,7,3′,4′-tetrahydroxyflavan-(4β-8-catechin (5), 2α,3α-epoxy-5,7,3′,4′-tetrahydroxyflavan-(4β−8)-epicatechin (6), 2β,3β-epoxy-5,7,3′,4′-tetrahydroxyflavan-(4α-8)-epicatechin (7), exhibited moderate antioxidant activities.