Li3Fe2(PO4)3 is interesting because of its technological application and environmentally benign nature. Nanocrystalline Li3Fe2(PO4)3 is synthesized by a solution combustion technique. The role of fuels/complexing agents in deciding the structural parameters and ac electrical behavior is investigated in this study. Antiferromagnetic nature and direct bandgap energy of 3.09 eV are recognized in the material. Enhanced conduction is established through mobility of Li+ ion in four co-ordination in the modified monoclinic symmetry and high temperature stability through orthorhombic symmetry. Quality of electrical data is confirmed through a Kramers-Kronig test and electrical relaxation parameters are obtained from modulus analysis. Scaling analysis of modulus data confirmed the time-temperature superposition principle.