Owing to its high surface area and high surface charge density, clay, either contaminated with heavy metal ions or modified with organic additives as barrier materials, is difficult to assess and monitor. Complex dielectric permittivity (κ*) showed promising potential in tackling the above issues. In this study, the complex dielectric permittivity (κ*) of clays modified with a surfactant, four polymers, and four metal ions was measured at frequencies from 0.2-20 GHz. With the addition of polymer and metal ions, increasing frequency caused a slight decrement in real permittivity but a significant decrement in effective permittivity. A modified linearity polynomial equation, which considered the particle conductivity, was developed to fit the relationship between effective conductivity (σeff) and porosity ranging from 0.7 to 1.0. A three-dimensional Cole-Cole plot (κ'-κeff″-w) shows Cole-Cole circle expansion at higher water content. The resonance strength of modified clays was observed to increase with water content, which suggests that the number of water molecules in the diffuse layer of polymer or metal ions saturated clay increased. However, sorbed polymer and metal ions have an insignificant influence on the resonance time τs and stretching exponent 1-α. κ* can provide nondestructive characterization of metal or polymer modified clays.