Sorption to soils/sediments is an underlying process affecting the fate, transport, degradation and bioavailability of organic compounds in the environment. Soil/sediment micropores are an important factor influencing the slow sorption-desorption of these chemicals. As a result, it is essential to study and understand the soil pore structure and micropores. This article reviews recent research advances in the characterization of soil/sediment micropores and their impacts on the behavior of organic compounds, including the soil pore structure and existence forms of soil/sediment micropores, the characterization of soil/sediment micropores, the determination of pore size distribution, the dynamics and mechanisms of slow sorption-desorption, as well as the future research directions. This review will provide a valuable and fundamental basis for bioremediation of soils contaminated by organic compounds and for risk assessment.