This work investigates the composition and morphology of films of poly(3-hexylthiophene) (P3HT), polyfluorene co-polymer poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2′,2″-diyl) (F8TBT) and blends thereof that are used in efficient all-polymer solar cells. Ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS) studies on thin polymer and blend films on ZnO substrates reveal the existence of a 1–2 nm thick P3HT layer at the top surface of the blend films. XPS depth profiling studies reveal a density wave (λ ≈ 70 nm) originating from the air interface. As no preferential accumulation is observed at the bottom interface with ZnO, the composition at this interface is consistent with the original composition of the blend solution prior to spin-coating. The morphology of this buried interface was studied by means of atomic force microscopy (AFM) and revealed that upon annealing the average domain size increases slightly (from 27 nm to 40 nm). It is observed that the photovoltaic performance of such inverted hybrid device improves upon annealing, however we believe this to mostly be a result of increased crystallinity in the P3HT domains leading to improved charge transport in the device, rather than changes in the blend phase separation.