In the present chapter we discuss the complex mixing behaviour of plasma membrane lipids. To do so, we first introduce the plasma membrane and membrane mixtures often used to model its complexity. We then discuss the nature of lipid phase behaviour in bilayers and the distinction between these phases and other manifestations of non-random mixing found in one-phase mixtures, such as clusters, micelles and microemulsions. Finally, we demonstrate the applicability of Gibbs phase diagrams to the study of increasingly complex model membrane systems, with a focus on phase coexistence, morphology and their implications for the cell plasma membrane.