A hole-collecting interlayer layer for organic solar cells, NiO, processed by atomic layer deposition (ALD) was studied. ALD-NiO film offered a novel alternative to efficient hole-collecting interlayers in conventional single-junction organic solar cells. Next, surface modifications with aliphatic amine group containing polymers for use as electron-collecting interlayers were studied. Physisorption of the polymers was found to lead to large reduction of the work function of conducting materials. This approach provides an efficient way to provide air-stable low-work function electrodes for organic solar cells. Highly efficient inverted organic solar cells were demonstrated by using the polymer surface modified electrodes. Lastly, charge recombination layers of the inverted tandem organic solar cells were studied. Efficient charge recombination layers were realized by using the ALD and the polymer surface modification. The charge recombination layer processed by ALD provided enhanced electrical and barrier properties. Furthermore, the polymer surface modification on the charge recombination layers showed large work function contrast, leading to improved inverted tandem organic solar cells. The inverted tandem organic solar cells with the new charge recombination layer showed fill factor over 70% and power conversion efficiency over 8%.