Nigricanoside A, isolated from the green alga Avrainvillea nigricans, is a structurally unique natural product in which two fatty acids, galactose, and glycerol are connected with ether linkages. Its dimethyl ester showed potent antitumor activities to cancer cell lines. The structure determination of nigricanoside A has not been solved due to the limited availability of this natural product. In this review, the structure elucidation of nigricanoside A by total synthesis is described.