Lithium-excess cathode materials can deliver high capacity and lead to high energy density. Lithium-excess cathode materials are categorized as “ordered” and “disordered” on the basis of order/disorder between Li and TM ions sites. Compared to the stoichiometric disordered materials, which show very poor capacity, Lithium-excess disordered materials exhibit high gravimetric capacities. Ordered Lithium-excess materials follow the conventional hopping pathways similar to that of Lithium cobalt oxide and disordered Lithium-excess materials follow percolation-type diffusion pathways. So, a comparative Lithium diffusion study between ordered and disordered Lithium-excess materials using muon spin relaxation experiments would give a deeper insight into the diffusion mechanism in Lithium-excess materials and thereby we attempt to understand their electrochemical behavior.