Heating and cooling thermograms of unsaturated MGDG samples isolated from the leaves of Vicia faba are surprisingly featureless. This reflects the low enthalpies associated with phase transitions in highly unsaturated lipids and the fact that these transitions, in the case of MGDG, are to a large extent masked by those associated with the freezing and melting of ice. Careful choice of thermal heating/cooling regimes, combined with the use of real-time X-ray diffraction and freeze-fracture measurements, permits a detailed analysis of the phase behaviour of the system. The phase behaviour of unsaturated MGDG samples is shown to be basically similar to that seen in saturated MGDG samples. The lipid which exists in the inverted hexagonal (HexII) liquid crystal phase at room temperature forms a highly disordered lamellar gel (L beta) phase on cooling to temperatures below about -15 degrees C. On reheating, this first reorganizes at a temperature of about -10 degrees C to form a well-defined Lc1 phase. Above about -2 degrees C, this melts to re-form the HexII phase. Samples re-cooled from temperatures between -2 degrees C and 14 degrees C revert directly to the Lc1 phase while samples cooled from higher temperatures form the L beta phase. This reflects the fact that the former samples contain small amounts of unmelted Lc1 phase lipid. The implications of these observations are discussed in terms of the general problems associated with the measurement of low-temperature phase behaviour of membrane lipids.