α-/β-Galactosylceramide (GalCer) and glucosylceramide (GlcCer) derivatives having a radical label at the 6-C-position suitable for electron paramagnetic resonance spectroscopic studies were synthesized by a diversity-oriented strategy that is highlighted by the efficient glycosylation of a lipid precursor and late-stage ceramide assembly to enable lipid diversification. The strategy was also utilized to synthesize natural α-/β-GalCers and GlcCers. Furthermore, the involved azido-intermediates are flexible platforms to access various other GalCer and GlcCer derivatives.