The progress in the development and understanding of interfacial materials for organic photovoltaics (OPV) is reviewed. The proper choice of interface materials is a must for highly efficient and stable OPV devices and has become a significant part of the OPV research today. Interface materials are either non-conducting, semiconducting or conducting layers which not only provide selective contacts for carriers of one sort, but can also determine the polarity of OPV devices, affect the open-circuit voltage, and act as optical spacers or protective layers. In this review both inorganic and organic interface materials are discussed with respect to their function in the OPV device.