Polyphosphorylated and perphosphorylated hexopyranose monosaccharides and disaccharides were synthesized from parent or partially protected carbohydrates as potential allosteric effectors of hemoglobin. A study toward the construction of seven- and eight-membered cyclic pyrophosphates was also performed on the sugars which had the proper orientation, protection, and number of phosphates. All final compounds were tested for their efficiency on oxygen release from human hemoglobin. Several compounds presented higher potency than myo-inositol hexakisphosphate, which is the most efficient of the known allosteric effectors of hemoglobin. Structure-activity relationships were analyzed. The affinity and efficiency depend on the number of phosphates attached to the carbohydrate skeleton and are related primarily to the number of negative charges present. Other effects operate, but play a lesser role.