Lipid membranes composed of monogalactosyldiacylglycerol (MGDG) and dimyristoylphosphatidylcholine (DMPC) were studied by means of NMR spectroscopy. The macroscopic phase behaviour was investigated by ³¹P NMR under stationary conditions, whereas microscopic properties such as segmental ordering were probed by two-dimensional ¹H-¹³C separated local field experiments under magic-angle spinning conditions. Our results clearly show that ordering/disordering effects occur for the headgroups as well as for the acyl chains when the sample composition is varied. In particular, the ¹H-¹³C dipolar couplings within the galactose headgroup of MGDG exhibited significant concentration dependence.