Thin film Si:O alloys have been grown by plasma enhanced chemical vapor deposition, as intrinsic or highly doped (1 to 5 at. % of B or P dopant) layers. UV-visible/near-infrared spectroscopy revealed a great dependence of the absorption coefficient and of the optical gap (Eg) on the dopant type and concentration, as Eg decreases from 2.1 to 1.9 eV, for the intrinsic or highly p-doped sample, respectively. Thermal annealing up to 400 °C induces a huge H out-diffusion which causes a dramatic absorption increase and a reduction of Eg, down to less than 1.8 eV. A prototypal solar cell has been fabricated using a 400 nm thick, p-i-n structure made of Si:O alloy embedded within flat transparent conductive oxides. Preliminary electrical analyses show a photovoltaic (PV) effect with an open circuit voltage of 0.75 V and a spectral conversion efficiency blue-shifted in comparison to a-Si:H based cell, as expected …