AbstractOctamolar tosylation of sucrose with p‐toluenesulfonyl (tosyl)chloride has been re‐examined under different conditions to obtain octa‐O‐tosyl sucrose as a single entity. It was observed that tosylation of sucrose with 8 moles of tosyl chloride in pyridine at 0°C, ‐5°C and ‐15°C afforded octa ‐O‐tosyl sucrose, hepta‐O‐tosyl sucrose, hexa‐O‐tosyl sucrose and penta‐O‐tosyl sucrose respectively in varying amounts. The products obtained were purified by column chromatography and the structures of the chromatographically pure tosyl esters were confirmed by high resolution 1H NMR spectra of their respective acetates.