Mannosylerythritol lipid (MEL) has attracted much attention as an environmentally benign and biocompatible material in many research fields due to its significant biochemical and physiological properties. However, heterogeneity always exists in MEL obtained from microbial products with respect to the chain length of the fatty acids. In this context, the total synthesis of the 20 members of MEL was effectively and stereoselectively achieved using our boron-mediated aglycon delivery (BMAD) method. In addition, structure-function relationship (SFR) studies of antibacterial activity, self-assembling properties, and recovery effects on damaged skin cells have been conducted, and these results are introduced in this mini-review article.