Molybdenum oxide (MoOx) has been shown to act as an efficient hole extraction layer in organic photovoltaic (OPV) devices. However, exposing MoOx films to air is problematic as it is hygroscopic; the uptake of moisture having a negative impact on its electronic properties. Here, we use spectroscopic ellipsometry to characterise the uptake of water, and fabricate PCDTBT:PC70BM based OPVs to determine its effects on device performance. We then show that thermally annealing MoOx reduces its hygroscopicity, permitting it to be processed in air. Using this process, we create air-processsed OPVs having PCEs (power conversion efficiencies) of up to 5.36%.