In this paper, we present a study of silicon surface passivation based on the use of spin-coated hybrid composite layers. We investigate both undoped poly(3,4-ethylenedioxythiophene)/poly-(styrenesulfonate) (PEDOT:PSS), as well as PEDOT:PSS functionalized with semiconducting oxide nanomaterials (TiO2 and SnO2). The hybrid compound was deposited at room temperature by spin coating-a potentially lower cost, lower processing time and higher throughput alternative compared with the commonly used vacuum-based techniques. Photoluminescence imaging was used to characterize the electronic properties of the Si/PEDOT:PSS interface. Good surface passivation was achieved by PEDOT:PSS functionalized by semiconducting oxides. We show that control of the concentration of semiconducting oxide nanoparticles in the polymer is crucial in determining the passivation performance. A charge carrier lifetime of about 275 μs has been achieved when using SnO2 nanoparticles at a concentration of 0.5 wt.% as a filler in the composite film. X-ray diffraction (XRD), scanning electron microscopy, high resolution transmission electron microscopy (HRTEM), energy dispersive x-ray in an SEM, and μ-Raman spectroscopy have been used for the morphological, chemical and structural characterization. Finally, a simple model of a photovoltaic device based on PEDOT:PSS functionalized with semiconducting oxide nanoparticles has been fabricated and electrically characterized.