Recent molecular studies have focused on the properties of self‐aggregating systems such as monolayers and bilayers, which are important and well‐known membrane models. This chapter focuses on the effect of molecular chirality and polarity of lipids and glycerolic amphiphiles, which are useful to study as membrane mimetic molecules. It reviews recent experimental observations and molecular understanding of the effect of chirality and polarity on the aggregate morphology of amphiphiles like lipids and glycerolic headgroup amphiphiles. The chapter describes the results of the theoretical study of dipolar interactions. Dipolar interactions in monolayers can have a subtle temperature dependence. It is largely accepted that the shape transition is governed by the competition between the shape‐dependent dipolar repulsion, which favors elongated shapes, and the line tension between the condensed phase domain and the surrounding fluid phase, which favors compactness of the domain. © 2008 John Wiley & Sons, Inc.