The diffusion of charged species in solids is a very important part of the study of the electrical properties of materials. Electrical measurements using alternating current (ac) impedance is a powerful technique to study diffusing species in metal oxides as well as polymers. Three case studies are being presented here whereby the electrical properties of LiTaO3, Poly[2-methoxy-5-(2’-ethylhexyloxy)-(p-phenylenevinylene)] (MEH-PPV) and its composite are being studied using the same ac impedance technique. LiTaO3 is a metal oxide while MEH-PPV is a polymer. They are very different and therefore present very good examples for the versatility and power of ac impedance method. Electrical parameters such as conductivity and conduction behaviours of the conducting species can be extracted from the studies. The kinetics of the diffusing species can be elucidated by using proper analytical techniques.