The U.S. Department of Agriculture (USDA) pepper (Capsicum spp.) germplasm collection contains several thousand members or accessions. Many of these species and cultivars have not been analyzed for their concentrations of ascorbic acid, capsaicin, and total phenolic compounds, which are important antioxidants having a number of benefits for human health. The objective of this investigation was to select candidate accessions of hot pepper having high concentrations of ascorbic acid, capsaicin, free sugars, and total phenols for use as parents in breeding for these compounds. Seventeen accessions of pepper from the core Capsicum germplasm collection (four accessions of Capsicum chinense; five accessions of C. baccatum; six accessions of C. annuum; and two of C. frutescens) were field grown and their mature fruits were analyzed for their antioxidant composition. Concentrations of these compounds tended to be higher in C. chinense and C. baccatum, than in C. annuum and C. frutescens. Across all accessions the concentration of total phenols was correlated with ascorbic acid (r = 0.97) and free sugars (r = 0.80). Concentrations of total phenols (1.4, 1.3, and 1.3 mg g⁻¹ fruit) and ascorbic acid (1.6, 1.2, and 1.3 mg g⁻¹ fruit) were significantly greater in PI-633757, PI-387833, and PI-633754, respectively, compared to other accessions analyzed. Total capsaicinoids concentrations were greatest (1.3 mg g⁻¹ fruit) in PI-438622 and lowest (0.002 mg g⁻¹ fruit) in Grif-9320. The great variability within and among Capsicum species for these phytochemicals suggests that these selected accessions may be useful as parents in hybridization programs to produce fruits with value-added traits.