Citric acid assisted solution combustion technique is explored for synthesis of supervalent Cu2+/Mg2+ ion doped LiNiPO4 system. XRD, FT-IR and microscopy studies confirmed the formation of a well crystallized material at low concentration of dopants. Ionic conductivity increases for lower concentrations of dopants due to the increased channel size for Li+ diffusion. Owing to inherent anti-site defects, ionic conductivity decreases with increase of dopant concentration. Magnetic studies are explored for confirmation of antiferromagnetic nature of ions. Wagner polarization method is used to elucidate the negligible contribution of electrons to total conductivity. (C) 2013 Elsevier Ltd. All rights reserved.