Microbial processes can affect the environmental behavior of priority radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes and can contribute to the remediation of radionuclide-contaminated land. Underlying mechanisms that can control radionuclide solubility in biogeochemical systems can range from biosorption and biomineralization process, through direct (enzymatic) and indirect redox transformations. The mechanisms of enzyme-mediated reduction of problematic actinides, in principal, uranium (U), but including neptunium (Np), plutonium (Pu) and Americium (Am), are described in this review. In addition, the mechanisms by which the fission products technetium (Tc), cesium (Cs), and strontium (Sr) are removed from a solution by microorganisms are also described. The present review discusses the status of these microbiological processes, and the potential for cost-effective and scalable in situ remediation of radioactive waste.