The foaming and emulsifying properties of a range of sucrose stearates were studied by measuring the content of monoester, diester, polyester as well as their hydrophile-lipophile balance (HLB) values. The composition and functional propertiesrelationship has been revealed; furthermore, an enzymatic synthesis of mono-sucrose stearate was completed, in a regio-selective method by using sucrose and stearic acid ethyl ester as the substrates, in the presence of phase transfer catalyst (myristyltrimethylammonium bromide). Thephysico-chemical properties of the associate product were measured. Results showed that the HLB values were mainly determined by the content of sucrose stearate monoester, a significant correlation was observed. As the lower HLBvalues as well as content of sucrose stearate monoester usually resulted in decreased foaming ability, foam stability and emulsion stability of the series of sucrose stearate, however, the emulsifying ability was observed to increase prior to decrease in this process. The structure of mono-sucrose stearate synthesized by this work has been confirmed by ¹H-NMR, ¹³C-NMR and ESI-MS with a HLB value 14.90, its foaming ability, foam stability and emulsifying ability as well as emulsion stability were also evaluated.The present work provided a theoretical basis for the application and green synthesis of sucrose stearates.