In this article, we investigated the role of potassium and Lithium hydroxide (KOH & LiOH) as precipitating agents on the physiochemical properties and electrochemical performance of MgCo2O4. Uniform cubic particles were obtained using lithium hydroxide. When LiOH was used as precipitating agents, discrete nanoparticles with uniform particle size were obtained. Whereas KOH as precipitating agent resulted in more agglomerated particles with non-uniform size distribution. After testing, we found that MgCo2O4 nanostructures prepared with LiOH showed high initial discharge/charge capacity of 1384/1013 mA h g−1 at current density of 60 mA g−1, and retained a high reversible capacity of 899 mA h g−1 over 50 cycles, which was superior in comparison to the electrochemical performance of the MgCo2O4 prepared using KOH as precipitating agent. The high electrochemical performance can be attributed to the small particle size and crystallinity of MgCo2O4 obtained using LiOH.