NaxLi1-xFeSi0.03P0.97O4/C (NLFSP) composites material with variations of Na doping (x=0, 0.01, 0.03, 0.05) have been successfully synthesized by solid state process. In this synthesized of cathode material used raw material are Li2CO3, NaNO3, FeC2O4, (NH4)2HPO4, SiO2 and Glucose (C6H12O6) as carbon source for material coating. The aims to of this research to determine the effect of Na doping variations on the NaxLi1-xFeSi0.03P0.97O4/C composites material in terms of its structure and electrical properties. The characterization of this research were XRD, PSA, SEM-EDX, and LCR Meter tests. The diffraction pattern of XRD has shown that all samples have formed an olivine LiFePO4 phase with orthorhombic crystal structure and Pnma space group which indicates that carbon coating does not change LiFePO4 structure. PSA and SEM data analysis have shown that the higher concentration of Na doping obtained the average distribution of smaller particle sizes. The electrical conductivity obtained from the highest LCR Meter characterization is 7.48 × 10-6 S/cm in the LFP5 sample (NaxLi1-xFeSi0.03P0.97O4/C with x = 0.05) and the lowest electrical conductivity is 1.93 × 10-7 S/cm in the LFP0 sample (NaxLi1-xFeSi0.03P0.97O4/C with x=0).