Pigeon pea is an important and multiuse grain legume crop, and its leaves are a very valuable natural resource. To obtain a high-quality biological resource, it is necessary to choose the excellent cultivar and determine the appropriate harvest time. In this study, the variation in contents of main active components and antioxidant activity in leaves of six pigeon pea cultivars during growth were investigated. The level of each individual active component significantly varied during growth, but with a different pattern, and this variation was different among cultivars. Flavonoid glycosides orientin, vitexin, and apigenin-6,8-di-C-α-L-arabinopyranoside showed two peak values at mid-late and final stages of growth in most cases. Pinostrobin chalcone, longistyline C, and cajaninstilbene acid showed remarkablely higher values at the mid-late stage of growth than at other stages. Pinostrobin had an extremely different variation pattern compared to other active components. Its content was the highest at the earlier stage of growth. Principal component analysis (PCA) revealed that vitexin and apigenin-6,8-di-C-α-L-arabinopyranoside were mainly responsible for distinguishing cultivars analyzed. In a comprehensive consideration, the leaves should preferentially be harvested at the 135th day after sowing when the level of active components and antioxidant activity reached higher values. Cultivars ICP 13092, ICPL 87091, and ICPL 96053 were considered to be excellent cultivars with high antioxidant activity. Our findings can provide valuable information for producing a high-quality pigeon pea resource.