D-glycero-L-galacto-Octulose and L-glycero-L-galacto-octulose accumulated when leaves of Kenland red clover (Trifolium pratense) were allowed to imbibe solution of D-gulose or D-xylose and L-mannose or L-arabinose, respectively. The octuloses were isolated and identified by paper chromatography and by oxidative degradations to the corresponding lower sugars. Assignments of the D and L configuration were made on the basis of optical rotation. It is suggested that formation of the octuloses from the hexoses and pentoses is mediated through transketolase and aldolase or transaldolase catalysis, respectively.