The presented study investigated the Induced Density of Interface States (IDIS) model at different polymer interfaces by using photoemission spectroscopy in combination with electrospray deposition. In recent years, organic electronics have attracted considerable attention due to their advantages of low-cost and easy-fabrication. The performance of such devices crucially depends on the energy barrier that controls the interface charge transfer. A significant effort has been made to explore the mechanisms that determine the direction and magnitude of charge transfer barriers in these devices. As a result of this effort, the IDIS model was developed to predict the energy alignment at metal/organic and organic/organic interfaces. The validity of the IDIS model on molecular interfaces was confirmed by the results of a series of experiments with small molecular materials, which are in good agreement with the theoretical calculations from the IDIS model. The charge neutrality level (CNL) and screening factor for various organic materials can be determined from the linear correlation between the hole injection barrier at metal/organic interface and the work function of its corresponding metal substrate, which stands as one of the most important features of the IDIS model. The study presented here explores whether the IDIS model is also valid for polymer interfaces. Two prototypical polymer materials: poly(3-hexylthiophene) (P3HT) and poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) were selected for the investigation. In the first part of this study, a series of metal/polymer interfaces were prepared using electrospray and investigated with photoemission spectroscopy. The linear relationship between the hole barriers extracted from the metal/polymer interface and the work function of its respective metal substrate suggests that the IDIS model is also valid for metal/polymer interfaces. The CNLs and the screening factors of P3HT and MEH-PPV are determined respectively. The experiment results are also discussed with regard to the Integer Charge Transfer (ICT) model. The comparison between the two models suggests that the IDIS model should be applied to interfaces prepared in vacuum while the ICT model works on interfaces with an ambient contamination layer present. The second part of the dissertation discusses the photoemission results of the MEH-PPV/P3HT heterojunction from the perspectives of the two models. The results indicate that the IDIS model is valid for polymer/polymer heterojunctions. The IDIS model more accurately predicted the measured orbital line up by using its principles for organic/organic heterojunction than the ICT model.