In this study, we fabricated a planar Si/PEDOT: PSS heterojunction solar cell using three different solvents—ethylene glycol, acetonitrile, and dimethyl sulfoxide—to find the best one. The fabricated samples were characterized by diffuse reflectance spectroscopy, scanning electron microscopy, X-ray diffraction, and current–voltage. Diffused reflectance spectrum analysis showed reduced reflectance compared to the bare silicon wafers. The absorbance spectrum shows the change in absorption of the Si-coated PEDOT: PSS which was more than a 50% increase in the UV region, and for the EG sample, there was a 20% increase in the entire visible spectrum. This indicates that the solvent plays a major role in the bandgap between the Si and Si/PEDOT: PSS. Scanning electron microscope (SEM) was used to examine the surface morphology of Si/PEDOT: PSS as agglomerated, island-formed surfaces and carbon-layered Si-PEDOT: PSS. Cross-sectional images show the thickness of the PEDOT: PSS layer on the silicon wafer surface. The X-ray diffraction (XRD) pattern shows the characteristic peaks for silicon (69.5°), and Si/PEDOT: PSS shows a forbidden Si (200) peak at 32°. Current–voltage measurements have shown the characteristic diode curve for all fabricated cells. This characteristic diode curve indicated the presence of a heterojunction. Ethylene glycol-containing cells showed current output as 0.2 μA with Voc of 0.2 V.