An array of ultra-long chain fatty acid sugar alcohol mono-esters, with behenic acid as an acyl representative and sugar alcohols altered from ethylene glycol, glycerol, erythritol, pentaerythritol, arabitol, xylitol to sorbitol, were enzymatically synthesized in high purity and selectivity. The molecular structures of synthetic compounds were confirmed by 1H NMR, FT-IR and MS analysis; and the thermal property was primarily characterized by DSC analysis. The molecular packing and thermal properties of synthetic sugar alcohol monobehenates (SAMBs) were investigated by Temp-Ramp-FT-IR. For in vivo application purpose, enzymatic lipolysis of synthesized SAMBs was examined by PPL (porcine pancreatic lipase) mediated in vitro digestion test; and improved resistance of most SAMBs to enzymatic lipolysis, in comparison to glycerol monopalmitate, was observed. FT-IR spectroscopic analysis of the thermotropic phase transitions of synthetic SAMBs turned out that the thermal collapse temperatures do not vary significantly as polar head alters, suggesting their thermostability are largely governed by hydrophobic interaction among alkanyl chains; while the size, property and volume of polar heads may determine the packing patterns. A systemic mapping of the structure-property-function relationship of SAMBs revealed the potential of these compounds for multi-purpose applications. Ethylene glycol and glycerol mono-behenates enable orthorhombic packing, which could find application in cosmetic formulation; and sorbitol mono-behenate is capable to form stable surfactant-free nanoparticles, which could be excellent excipient of solid lipid nanoparticles as a delivery cargo of drugs and food ingredients.