The mobility of free charges and its localization mechanism has considerable effect on the dielectric properties of the materials. Therefore single crystal of Fe doped BaTiO3 and KTiOPO4 (KTP) which have predominantly electronic and ionic conductivity respectively were studied under external stresses like electric and magnetic field. The application of external magnetic field affects the hopping of electrons which lead to tuning of polaron losses in BaTiO3 whereas in case of KTP localization of K+ ions give rise to splitting of piezoelectric resonance and it can be tuned by external electric field. In the second part new phosphates of formula BaFeTi(PO4)3 and BiFe2(PO4)3 were synthesized to look for polarization property. However Bi3+ ions are not localized on their inversion symmetry site which is promising. Finally spinel Co3O4 was investigated under dielectric and Electron Paramagnetic Resonance spectroscopy which reveal an induction of polar state under external magnetic field.