Lipid membranes composed of monogalactosyldiacylglycerol (MGDG) and dimyristoylphosphatidylcholine (DMPC) were studied by means of NMR spectroscopy. The macroscopic phase behaviour was investigated by (31)P NMR under stationary conditions, whereas microscopic properties such as segmental ordering were probed by two-dimensional (1)H-(13)C 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 (1)H-(13)C dipolar couplings within the galactose headgroup of MGDG exhibited significant concentration dependence.