[reaction: see text] Naturally occurring phosphoinositide glycoconjugates are equipped with varied acyl residues that are important for their biological activity and biosynthesis. This paper reports that acylation at O2 of the myo-inositol moiety can be achieved by stereocontrolled ortho ester rearrangement. Coupling to homo- or heterodiacylated glycerols was achieved via phosphoramidite methods, and exhaustive debenzylation by transfer hydrogenation afforded the deprotected phosphoglyceroinositides. The latter can be kept in chloroform solution at room temperature for over two months without migration of the inositol acyl group.