The chemistry of sucrose is very challenging due to its eight hydroxyl groups, three of which are primary, with very similar reactivities, thus control of the chemoselectivity is a central issue. In this work, the selective formation of monounsaturated esters at the 6-position, by applying the Mitsunobu conditions for the selective esterification of sucrose, is reported. Also, the outcome of a number of mono-substitution reactions at positions 6 or 6', and di-substitution reactions at positions 6 and 6' have been explored. Mild and energy-efficient procedures, with short reaction times (5 to 10 min) using microwave irradiation have been developed, and the results compared with conventional procedures. In some cases, the use of microwave irradiation appeared to provide not only time saving but also improved selectivity.