The effects of scavenging 2, 2-diphenyl-2-picrylhydrazyl hydrate (DPPH) radicals and inhibiting low-density lipoprotein (LDL) oxidation, and phenolic quantities were used for the activity-guided separation to identify the effective components of litchi flower. The acetone extract of the flower with notable antioxidant capacities was suspended in water and sequentially partitioned with n-hexane, ethyl acetate (EA) and n-butanol. The EA partition with the highest phenolic levels and antioxidant capacities was subjected to silica gel column chromatography. Thirteen fractions (Fr. 1-13) were collected; Fr. 10-12 with higher phenolic levels and antioxidant effects were applied to Sephadex LH-20 column chromatography. Each fraction was further separated into three sub-fractions and the second ones (Fr. 10-II, 11-II, and 12-II) were the best, which two major compounds could be isolated by semi-preparative high performance liquid chromatography (HPLC). Through Mass (MS) and Nuclear Magnetic Resonance (NMR) measurements, they could be identified as (-)-epicatechin and proanthocyanidin A2. Their contents in the litchi flower were 5.52 and 11.12 mg/g of dry weight, respectively. The study was the first time to reveal the effective antioxidant components of litchi flower.