In phospho-olivine type structures with mixed cations (LiM1M2PO4), the octahedral M1 and M2 sites that dictate the degree of intersites order/disorder play a key role in determining their electrochemical redox potentials. In the case of LiFexMn1-xPO4, for example, in micrometer-sized particles synthesized via hydrothermal route, two separate redox centers corresponding to Fe(2+)/Fe(3+) (3.5 V vs Li/Li(+)) and Mn(2+)/Mn(3+) (4.1 V vs Li/Li(+)), due to the collective Mn-O-Fe interactions in the olivine lattice, are commonly observed in the electrochemical measurements. These two redox processes are directly reflected as two distinct peak potentials in cyclic voltammetry (CV) and equivalently as two voltage plateaus in their standard charge/discharge characteristics (in Li ion batteries). On the contrary, we observed a single broad peak in CV from LiFe0.5Mn0.5PO4 platelet-shaped (∼10 nm thick) nanocrystals that we are reporting in this work. Structural and compositional analysis showed that in these nanoplatelets the cations (Fe, Mn) are rather homogeneously distributed in the lattice, which is apparently the reason for a synergetic effect on the redox potentials, in contrast to LiFe0.5Mn0.5PO4 samples obtained via hydrothermal routes. After a typical carbon-coating process in a reducing atmosphere (Ar/H2), these LiFe0.5Mn0.5PO4 nanoplatelets undergo a rearrangement of their cations into Mn-rich and Fe-rich domains. Only after such cation rearrangement (via segregation) in the nanocrystals, the redox processes evolved at two distinct potentials, corresponding to the standard Fe(2+)/Fe(3+) and Mn(2+)/Mn(3+) redox centers. Our experimental findings provide new insight into mixed-cation olivine structures in which the degree of cations mixing in the olivine lattice directly influences the redox potentials, which in turn determine their charge/discharge characteristics.