During the past four decades it has been recognized that natural disruption of the U and Th decay chains, resulting in the separation of parent and daughter nuclides, occurs as a consequence of geochemical processes acting in the near-surface environment. This realization has lead to a rapid growth in the application of the naturally occurring radioactive disequilibria diversifying broadly to touch upon a wide spectrum of problems in earth sciences.This paper is a brief review of the subject and addresses a number of issues concerning (1) physico-chemical processes responsible for fractionation of radionuclides in the decay series, (2) the range of observed radioactive disequilibrium in nature, (3) implications in terms of relative mobilities of U, Th, Ra and their daughters in the geosphere, and (4) examples of the application of these concepts to studies of paleoclimate, dating of old groundwaters, and rock/water interaction processes.This review concludes that the concept of radioactive disequilibrium in naturally occurring decay series is a powerful isotopic tool with applications in both terrestrial and marine environments over timescales of up to one million years.