© 2018 The Royal Society of Chemistry. Anions have often been considered to act essentially as electron donors or acceptors in molecular conductors. However there is now growing evidence that they play an essential role in directing the structural and hence electronic properties of many of these systems. After reviewing the basic interactions and different ground states occurring in molecular conductors we consider in detail how anions influence the structure of donor stacks and often guide them toward different types of transitions. Consideration of the Bechgaard and Fabre salts illustrates how anions play a crucial role in directing these salts through complex phase diagrams where different conducting and localized states are in competition. We also emphasize the important role of hydrogen bonding and conformational flexibility of donors related to BEDT-TTF and we discuss how anions have frequently a strong control of the electronic landscape of these materials. Charge ordering, metal to metal and metal to insulator transitions occurring in these salts are considered.