Two major anthocyanins (A1 and A2) were isolated from peels of the spears of Asparagus officinalis cv. Purple Passion. They were purified by column, paper and high-performance liquid chromatographic separations, and their structures were elucidated by high-resolution Fourier transform ion cyclotron resonance mass spectrometry (HR-FT-ICR MS), 1H, 13C and two-dimensional NMR spectroscopic analyses and either acid or alkaline hydrolysis, respectively. A1 was identified as cyanidin 3-[3''-(O-beta-d-glucopyranosyl)-6''-(O-alpha-l-rhamnopyranosyl)-O-beta-d-glucopyranoside], whereas A2 was cyanidin 3-rutinoside, which is widely distributed in higher plants. Oxygen radical absorbance capacity (ORAC) assays proved their high antioxidant activities.