Electrodeposition of selenium from 1-propyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide is reported. In situ UV-vis spectroelectrochemistry was used to investigate the reduction of diethyl selenite to form elemental selenium thin films from an ionic liquid-acetonitrile medium. Three reduction peaks of diethyl selenite were observed via cyclic voltammetry and are attributed to the stepwise reduction of the selenium precursor adsorbed on the electrode. The electrodeposition mechanism is influenced by both potential and time. Electrodeposition at -1.7 V vs Pt QRE resulted in the. deposition of elemental selenium nanoparticles that with time coalesced to form a continuous film. At reduction potentials more negative than -1.7 V the morphology of the deposit changed significantly due to the reduction of elemental Se to Se2-. In addition, p-type photoconductivity of the films was observed during the spectroelectrochemical measurements. X-ray diffraction and Raman spectroscopy confirmed that the deposited selenium films were amorphous. X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy confirm the films consisted of pure selenium with minor residual contamination from the precursor and ionic liquid.