This report describes the preparation, characterization, and coin cell prototype testing of new Li[Fe1/3Ni1/3Co1/3]PO4 high voltage olivine cathodes for lithium secondary batteries (LFNCPs) obtained by treating the precursors with Cu and Cu+C sources. The morphology, structure, interactions, and electrochemical properties of the obtained materials are extensively studied in order to elucidate the interplay in LFNCPs between graphite (C) and copper(II) carbonate (Cu) addition to the precursors and structural flexibility, relaxations, and electrochemical performance of obtained materials. In particular, the investigated LFNCPs cathodes are obtained by treating the reaction precursors with graphite nanoparticles and/or copper(II) carbonate. It is found that copper does not behave like a vicariant metal ion within the olivine structure of the cathodes, instead it forms segregated CuO nanoparticles which improve the charge-transfer kinetics during the charge/discharge processes of the cathode material. The graphite additive in precursors is found to decompose during the synthesis, resulting in an improved elasticity of the 3D structure of the olivine backbone. This increased structural flexibility facilitates the percolation of lithium ions along the 1D channels of the materials during the charge/discharge processes. Coin cell prototypes assembled with the proposed cathode materials show good specific capacities (>100mAhg−1), good specific energies (455mWhg−1), and a high working potential (>4.0V).