An architecture featuring carbon coated, interconnected nano-grains constructed with mesopores is developed for LiMnPO4 cathode material. This architecture facilitates enhanced lithium ionic and electronic transports; favours improved lithium storage performance. Mesoporous LiMnPO4/C electrode delivers discharge capacity of 140mAhg−1 at 0.05C using galvanostatic cycling mode. This best electrochemical response of LiMnPO4/C at constant current mode is complemented by diffusion studies using cyclic voltammetry and impedance spectroscopy. Further, the interdependence of lithium storage performance on carbon content, milling time (2, 4, 6 and 10h), grain size and porous characteristics (surface area, pore size and pore volume) is also discussed. Finally, the feasibility of LiMnPO4/C cathode is evaluated against Li4Ti5O12/C anode in a full cell.