The effect of platelet-activating factor (1-O-hexadecyl-2-acetyl-sn-glycero-3-phosphocholine, PAF) and two related molecules, 1-O-hexadecyl-sn-glycero-3-phosphocholine (LPAF) and 1-palmitoyl-sn-glycero-3-phosphocholine (LPC) on dielaidoylphosphatidylethanolamine (DEPE) lipid structure and polymorphism has been studied by differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) and P-31 nuclear magnetic resonance (P-31-NMR) spectroscopies. From the interaction of these molecules with DEPE it is concluded that all of them stabilize the lamellar phase with respect to the hexagonal H(II) phase and this effect is clear even at concentrations of these compounds as low as 1 mol%. It is also shown that, although they perturb the gel to liquid-crystalline phase transition of DEPE up to a similar extent, fluidizing the membrane, PAF but not LPAF or LPC, induces the presence of more than one peak in the calorimetric profile. Moreover, FTIR data indicate that lateral phase separations formed by PAF-rich phases are taking place. Remarkably, DELTAH of the main transition decreases at concentrations lower than 2 mol% but remains nearly constant up to 30 mol%. P-31-NMR measurements showed that all these molecules were capable of inducing isotropic signals in the spectra produced by molecules associated to membranes before micellization of the vesicles.