We discuss here bulk-heterojunction polymer solar cells with engineered interfaces to achieve desired phase separations (vertical and horizontal), molecule orientations, ohmic contacts, and electronic properties for device performance maximization, and to enhance the device durability by eliminating corrosive interfacial layers. The strategies discussed include development of novel interfacial layers such as self-assembled organic layers and inorganic metal oxide layers, and using inverted cell architectures. Interface engineering leads to optimal active layer morphologies and to polymer π- orientation, as well as maximum open circuit voltage. Using p-type NiO as the anode hole transporting/electron blocking layer results in dramatically enhanced device performance of P3HT/PCBM polymer solar cells with PCEs up to 5%. Electrical property and surface morphology investigations of NiO elucidate the mechanism for the enhanced performance. Other novel interfacial materials such as self-assembled organic monolayers and graphene oxide (GO) have also been incorporated into polymer solar cells to achieve comparable PCEs with improved device stability. Using ZnO as electron transporting/hole blocking layer and employing an inverted device architecture, polymer solar cells achieve desired molecule π-orientation and vertical phase separation, therefore extremely high fill factors and promising power conversion efficiencies. In addition to interfacial layer materials, active layer components with state-of-the-art device performance, both polymer and small molecule developed in this laboratory, will also be discussed.