Sugar esters of fatty acids are bio-based surfactants that were synthesized by transesterification of table sugar (sucrose) with stearic acid methyl ester (SAME) in high yield and purity using an optimized microwave-assisted method. The maximum surfactant product yield of 88.2% was obtained by combining reactants with potassium methoxide and irradiating the mixture with microwaves to achieve an ideal reaction temperature of 132 °C over 21 min. The synthetic procedure described herein minimized undesirable sugar pyrolysis as evidenced by retention of white color characteristic of a pure bio-based surfactant product. The experiment implemented Box–Behnken design for response surface methodology to refine reaction parameters for optimal product yield. The following parameters were augmented: the irradiation time, the mole ratio of catalyst to sucrose, and temperature.