Various models of the complex formation between polyelectrolyte chains and oppositely charged macroions are reviewed. In recent years, a great deal of knowledge of the multitude of possible polyelectrolyte conformations at the macroion surface has been accumulated, which consequently has led to increasing interest in using such complexes in the design of nanomaterials. This review focuses on key studies relating to the effects of various physico-chemical parameters on complex formation and areas for future research are identified.