Mechanisms of charge transport between the interconnector and its neighboring layers in tandem organic photovoltaic cells have been systematically investigated by studying electronic properties of the involving interfaces with photoelectron spectroscopies and performance of the corresponding devices. The results show that charge recombination occurs at HATCN and its neighboring hole transport layers which can be deposited at low temperature. The hole transport layer plays an equal role to the interconnector itself. These insights provide guidance for the identification of new materials and the device architecture for high performance devices.