Stevia rebaudiana Morita, which produces a higher ratio of rebaudioside A relative to stevioside, was developed as a cultivar by selective breeding of S. rebaudiana Bertoni. The structures of 21 compounds (termed SG1-20) extracted from the leaves with hot water were characterized by ESI-MS/MS, ¹H- and ¹³C-NMR and/or chemical analyses after separation by HPLC on an Amide-80 column. Among them, ten compounds (about 7% of the total) were found to be new steviol glycosides that contained the following sugar chains linked at C13 (R₂) and C19 (R₁) of the aglycon steviol. SG4: R₁ = H-, R₂ = Rhaα1-2(Glcβ1-3)Glcβ1-; SG7: R₁ = Glcβ1-, R₂ = Glcβ1-3Glcβ1-; SG12: R₁ = Glcβ1-3Glcβ1-, R₂ = Glcβ1-2(Glcβ1-3)Glcβ1-; SG14: R₁ = Glcβ1-, R₂ = Glcβ1-3Rhaα1-2(Glcβ1-3)Glcβ1-; SG15: R₁ = Glcβ1-, R₂ = Glcβ1-6Glcβ1-2(Glcβ1-3)Glcβ1-; SG16-I: R₁ = Glcβ1-2Glcβ1-, R₂ = Rhaα1-2(Glcβ1-3)Glcβ1-; SG16-II: R₁ = Rhaα1-2Glcβ1-, R₂ = Glcβ1-2(Glcβ1-3)Glcβ1-; SG17: R₁ =, R₂ = Glcβ1-2(Glcβ1-3)Glcβ1-; SG19: R₁ = Rhaα1-2(Glcβ1-3)Glcβ1-, R₂ = Glcβ1-2(Glcβ1-3)Glcβ1-; SG20: R₁ = Glcβ1-3Rhaα1-2(Glcβ1-3)Glcβ1-, R₂ = Glcβ1-2(Glcβ1-3)Glcβ-. Eleven compounds were previously known steviol glycosides, among which rebaudioside A (61.6% of total), stevioside (9.2%) and rebaudioside C (7.5%) were predominant.