High photovoltaic device performance is demonstrated in ambient-air-processed bulk heterojunction solar cells having an active blend layer of organic poly(3-hexylthiophene) (P3HT): [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM), with power conversion efficiencies as high as 4.1% which is comparable to state-of-the-art bulk heterojunction devices fabricated in air-free environments. High-resolution transmission electron microscopy is combined with detailed analysis of electronic carrier transport in order to quantitatively understand the effects of oxygen exposure and different thermal treatments on electronic conduction through the highly nanostructured active blend network. Improvement in photovoltaic device performance by suitable post-fabrication thermal processing results from the reduced oxygen charge trap density in the active blend layer and is consistent with a corresponding slight increase in thickness of an similar to 4 nm aluminum oxide hole-blocking layer present at the electron-collecting contact interface.