Lithium iron phosphate (LiFePO4) micro-particles (MPs) were synthesized under hydrothermal condition for fabrication of cathode materials based on LiFePO4 MPs/multi-walled carbon nanotube (MWCNT) nanocomposites. Influence of reaction time for the hydrothermal process on structural, morphological, and electrochemical behavior was investigated. Crystal quality was confirmed by X-ray diffraction (XRD) together with Raman analysis. Micrometer-scale seeds and capsule-shaped morphology were observed. Such nanocomposite cathodes based on LiFePO4 MPs/MWCNT were prepared by surface-engineered tape casting technique. The well-crystallized material composed of densely aggregated MPs and interconnected with MWCNTs led to excellent volumetric Li storage properties at a current rate of 0.1 mVs−1 between 2.5 to 4.3 V. However, the half-cell analysis does not show reasonable capacity values, which may be due to the larger particle size and morphology of synthesized LiFePO4, resulting in limiting ionic transportation and electronic conduction path.