Photoactive devices embedding MoS2 thin layers between indium tin oxide (ITO) and fluorine doped tin oxide have been prepared by electrodeposition of MoS2. In order to improve carrier transport capability, the interface between MoS2 and ITO has been engineered with the introduction of a thin MoO3 layer. The effect of MoS2 concentration in the electrodeposition solution has been investigated. The structure and the optical properties of electrodeposited MoS2 have been studied by Raman spectroscopy, UV–Vis measurements, and transmission electron microscopy. The photoelectric response has been investigated using a 630 nm laser as a function of the power and applied voltage. The device with MoO3 shows promising external quantum efficiencies, from ≈0.25% at zero bias up to ≈50% at a bias of 1.6 V.