The anionic conjugated polyelectrolyte, poly[3-(6-sulfothioatehexyl)thiophene] (P3Anionic), functions as a highly sensitive probe of membrane order, uniquely capable of sequentially detecting the three key phase transitions occurring within model phospholipid bilayers. The observed sensitivity is the result of charge-mediated, selective localisation of P3Anionic within the head-groups of the phospholipid bilayer