Cinnamomum osmophloeum Kaneh. is an indigenous tree species in Taiwan. In this study, phytochemical characteristics and antioxidant activities of ethanolic extracts from the twigs of C. osmophloeum were investigated for the first time. The extracts were obtained successively using liquid-liquid partition to yield n-hexane (Hex), ethyl acetate (EtOAc), n-butanol (BuOH) and water fractions. The antioxidant activities of C. osmophloeum twig extracts were examined using various antioxidant assays, such as DPPH, NBT, reducing power, lipid peroxidation using mouse brain homogenates, metal chelating ability, and photochemiluminescence (PCL). In addition, total phenolic contents were also determined. Results revealed that the BuOH fraction exhibited the best performance in DPPH assay, NBT assay, reducing power assay and lipid peroxidation using mouse brain homogenates assay. Furthermore, the BuOH fraction has the highest total phenolic contents (496.7 mg of GAE/g). Consequently, kaempferol-7-O-rhamnoside was also isolated from the antioxidative BuOH fraction and its activity was also confirmed. These results demonstrated that ethanolic extracts of C. osmophloeum twigs have excellent antioxidant activities and thus it has great potential as a source for natural health products.