A study was performed to assess the effect of controlling the reduction mechanism on Li2O entrainment in an electrolytic UO2 reduction process. The reduction mechanism was controlled by isolating the UO2 particles from the lead, eliminating the direct reduction mechanism. Cathode design made it possible to eliminate the direct UO2 reduction mechanism, as evidenced by the cathode potential, the result being indirect reduction via electrolytically produced Li metal. Characterization of the reduced product was achieved via acid-base titration to measure Li2O entrainment and thermogravimetry to measure reduction extent. Significantly increased entrainment was observed when the electrolytic UO2 reduction portion was eliminated compared to normal operation. In addition to the entrainment the representativeness of dip sampling, compared to cup sampling, was investigated. A statistically significant difference between Li2O concentration measurements from dip and cup samples was observed, dip samples measured 8 ± 3% less Li2O than cup samples.