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The pericarp of Litchi chinensis was reported to be a rich source of antioxidants. This study aimed to identify the chemical structures present in litchi pericarp with antioxidant activity. Four lignans, (+)-isolariciresinol 9-O-α-l-arabinopyranoside (1), burselignan 9-O-α-l-arabinopyranoside (2), (−)-secoisolariciresinol 9-O-α-l-arabinopyranoside (3), and sisymbrifolin (4), a chromane, 2α-methoxychroman-3α,5,7-triol (5), a benzophenone, garcimangosone D (6), and two sesquiterpenes, β-d-glucopyranosyldihydrophaseate (7) and citroside A (8) were isolated. Their structures were elucidated by spectroscopic methods. Compounds 1–3, 5, and 7 were new metabolites and the others were reported from this species for the first time. Among them, compounds 1–5 showed moderate antioxidant activity in ferric reducing antioxidant power (FRAP) and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging assays.