Magnesium-ion batteries represent promising environmentally sustainable energy-storage systems with higher energy densities than their lithium counterparts. In this work, the charge storage mechanisms of the olivine-related compound (Mg0.5Ni0.5)3(PO4)2 using Mg2+ and Li+ ions were investigated and compared for the first time when copper was chosen as the current collector. A comprehensive physicochemical and electrochemical characterization was performed on the pristine powder and electrodes at different states of charge. Although (Mg0.5Ni0.5)3(PO4)2 is electrochemically active, it undergoes irreversible conversion reactions in both Mg and Li chemistries. The conversion reactions proceed with an ionic exchange between structural Ni2+ and Mg2+ or Li+ cations, which results in the formation of sarcopside-Mg3(PO4)2, a Cu–Ni alloy and poorly crystalline Li3PO4, respectively. A capacity of 600 mA h g−1 was achieved with a Li metal counter electrode in the Li cell since the conversion reaction could go to completion. A capacity of 92 mA h g−1 was delivered in the Mg cell using an activated carbon counter electrode. These findings shed light on the fundamental mechanism of activity in olivine-related compounds, underlining the importance of performing systematic studies to unveil the complex interactions between both single-valent and multivalent ions with novel structures.