The impact of crystalline structure changes of sputtered ZnO interfacial layer on performances of inverted organic solar cells (OSCs) has been investigated. We find that the structural modification of the ZnO cathode interfacial layer, obtained by thermal annealing, plays a crucial role in the origin and solving of the S-curve in conjugated polymer/fullerene photovoltaics. Our results show that the crystallization (i.e. crystallites size) of poly(3hexylthiophene) (P3HT) evolves as a function of that of ZnO according to the annealing temperature. This evolution can directly impact the interfacial orientation and organization of the chains of P3HT at the ZnO buried interface. Such an ordered profile favors the vertical phase segregation and raises the carrier mobility, which explains the disappearance of the S-shape observed in current density-voltage device characteristics for annealing temperatures above 200 degrees C. These results adequately address recent research and provide an important insight into the interfacial layers of inverted OSCs. (C) 2014 Elsevier B.V. All rights reserved.