Na4MnV(PO4)3 is a sodium ion conducting material with a NASICON type crystal structure. This phase is not much known as an electrode material. The present work focuses on the sodium ion intercalation/de-intercalation mechanism and charge/discharge behavior of the material. The Na4MnV(PO4)3 is synthesized through a sol-gel process and characterized by XRD, SEM, and XPS. The structural analysis confirms the formation of a phase pure crystalline material with nanometric particle size which adopts a trigonal crystal structure. Galvanostatic intermittent titration technique (GITT) measurements indicate that Na4MnV(PO4)3 is electrochemically active having slanting voltage plateaus. Ex-situ and In-situ XRD analysis, as a function of sodium concentration, indicate that the intercalation/de-intercalation of sodium is associated with a single-phase reaction rather than a biphasic reaction when cycled between 1.5 and 4.5 V. The electrochemical measurements on composite electrodes, Na4MnV(PO4)3/CNTS (1 & 3 wt.%), show promising charge/discharge capacity (∼140 mAh/g), good cyclability (100% capacity retention after 40 cycles) and reasonable rate capability. The cyclic voltammetry (CV) and X-ray Photoelectron Spectroscopy (XPS) analyses indicate that the main contributions towards the activity of Na4MnV(PO4)3 can be attributed to the active of Mn2+/Mn3+ and V3+/V4+ redox couple with partial activity of V4+/V5+. The obtained results suggest that Na4MnV(PO4)3 is a promising electrode material which can be achieved better rate performance with long cycling stability and battery performance through engineering of the particle morphology and microstructure.