Synthesizing metal oxides through the sol–gel process provides a convenient way for forming a nanostructured layer in wide band gap semiconductors. In this paper, a unique method of introducing dopants into the metal oxide semiconductor is presented. The doped TiO2 is prepared by adding a Cs2CO3 solution to a nanocrystalline TiO2 solution that is synthesized via a non-hydrolytic sol–gel process. The properties of the TiO2:Cs layer are investigated and the results show stable nanostructure morphology. In addition to providing morphological stability, Cs in TiO2 also gives rise to a more desirable work function for charge transport in organic electronics. Polymer solar cells based on the poly(3-hexylthiophene) (P3HT): methanofullerene (PC70BM) system with the addition of a TiO2:Cs interfacial layer exhibit excellent characteristics with a power conversion efficiency of up to 4.2%. The improved device performance is attributed to an improved polymer/metal contact, more efficient electron extraction, and better hole blocking properties. The effectiveness of this unique functionality also extends to polymer light emitting devices, where a lower driving voltage, improved efficiency, and extended lifetime are demonstrated.