Molybdenum (Mo) is a refractory metal used principally as an alloying agent in steels, cast irons, and super alloys to enhance hardness, strength, toughness, wear and corrosion resistance and it is also widely used in catalytic applications, lubricants and pigments. The single electrodeposition of Mo from aqueous solutions cannot be achieved but Mo it can be co-deposited as an alloy with iron group metals (induced co-deposition). In this study, the electrodeposition of Mo/MoO x from dimethyl sulfoxide solutions on a copper substrate has been investigated. Different experimental electrodeposition parameters have been assessed (i.e., supporting electrolyte concentration and small amounts of water to the electrolytic bath) to analyze their influence on mechanism of induced Mo/MoO x deposition. Linear scan voltammetry has been used to follow up the electrodeposition of Mo/MoO x films. Film morphology has been characterized using scanning electron microscopy (SEM), compositional analysis was performed using X-ray photoelectron spectroscopy. Mo bearing films were also chemically characterized by ICP-OES analysis. An electrodeposition mechanism was developed and discussed.