In this review we present examples of using radioactive isotopes as probes to study functional materials of fundamental and applied interest presenting colossal magnetoresistance, multiferroic effects, and magnetostructural coupling. Most of the works exploit the hyperfine properties, Electric Field Gradient (EFG) and Hyperfine Magnetic Field (HMF), of these probes through Perturbed Angular Correlation (PAC) spectroscopy. The measurements were complemented with density functional theory calculations to model the relevant properties and correlate the EFG with the electric polarization. We also