The orientational order and rotational dynamics of 1-palmitoyl-2-[[2-[4-(6-phenyl-trans-1,3,5-hexatrienyl)phenyl]ethyl] carbon yl]-3-sn-phosphatidylcholine (DPH-PC) in dilinoleoylphosphatidylethanolamine (DLPE) and 1-palmitoyl-2-oleoylphosphatidylcholine (POPC) binary lipid mixtures were investigated. A previous study (Biochim. Biophys. Acta 731 (1983) 177) indicated that the empirical phase diagram of POPC/DLPE can roughly be divided into three zones. They are the lamellar (15% PC and higher), intermediate (5–15% PC) and inverted hexagonal (0–5% PC) phases. As the lipids changed from the lamellar to intermediate phase, the order parameter increased at all temperatures (1–50°C). On the contrary, the rotational diffusion decreased at high temperatures (20–50°C) but increased at low temperatures (1–10°C). These results indicate that the intermediate phase is in a stressed state at high temperatures but in a highly mobile amorphous state at low temperatures. As the lipid progressed fromthe intermediate toward hexagonal phase, the order parameter decreased abruptly at all temperatures. The ratio of order parameter in the intermediate phase to that in the hexagonal phase was calculated. This ratio was found to increase linearly with temperature, indicating that a distinct change in the packing symmetry of lipids occurred as temperature increased. From the intermediate to hexagonal phase, the rotational diffusion increased slightly at high temperatures but declined abruptly at low temperatures. These results further agreed with the stressed and amorphous natures of the intermediate phases as described above.