Sialic acids can be acetylated at the 4, 7, 8 and/or 9 position. Biological roles of these substitutions have been missed until recently because of their low abundance and lability to conventional purification methods. The recent advances in the analysis of sialic acids have allowed to demonstrate that O-acetylation has a selective but widespread distribution. The metabolism of acetylated sialic acids is under the control of two groups of enzymes, O-acetyl transferases and 9-O-acetyl esterases. O-acetyl transferases are difficult to purify, and furthermore, attempts at expression cloning have failed in isolating the true 9-O-acetyl transferase cDNA. This explains that the regulation of the selective expression of O-acetylated sialic acid in not completely understood. Acetylation of sialic acid is expressed on the outer most part of the carbohydrate moiety of membrane and secreted glycoconjugates. This particular location explains why this modification is involved in cell/cell interactions and in the non-immune protection of mucosa.