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 relationship between its composition and functional properties has been revealed. Furthermore, using sucrose and stearic acid ethyl ester as the substrates, mono-sucrose stearate was enzymatic synthesized in the presence of phase transfer catalyst (myristyltrimethylammonium bromide). The physico-chemical properties of the associate product were investigated. Results showed that the HLB values were decreased with the decreasing of the content of sucrose stearate monoester, which showing a significant correlation. The lower HLB values and lower 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 be increased prior to decreasing in this process. The structure of mono-sucrose stearate synthesized herein has been confirmed by 1H-NMR, 13C-NMR and ESI-MS with a HLB value of 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.