Polymethoxyflavones (PMFs) from citrus genus have been of particular interest because of their broad spectrum of biological activities, including antiinflammatory, anticarcinogenic, and antiatherogenic properties. There have been increasing interests in the exploration of health beneficial properties of PMFs in citrus fruits. Therefore, the isolation and characterization of PMFs from sweet orange (Citrus sinensis) peel will lead to new applications of the byproducts from orange juice processes and other orange consumption in nutraceutical and pharmaceutical products. In our study, eight hydroxylated PMFs, six PMFs, one polymethoxyflavanone, one hydroxylated polymethoxyflavanone, and two hydroxylated polymethoxychalcones were isolated from sweet orange peel and their structures were elucidated by various MS, UV, and different NMR techniques. Some of the hydroxylated PMFs and chalcones are newly isolated from sweet orange peel.