The radioactive contaminant plume in groundwater at the Karachai Lake site has been examined further. The source of pollution is the Karachai Lake which was used as a reservoir for liquid radioactive waste (LRW) from the Radiochemical Production Association “Mayak” (South Urals, Russia). Taking into account that colloid-facilitated transport of radionuclides can substantially increase the contaminant migration velocity, the composition and structure of colloid particles from the groundwater within the contaminant plume were studied. Sampling of groundwater was carried out in the observation well within the contaminant plume. Different fractions of colloid particles were extracted from the groundwater samples by sequential filtration through membranes with decreasing pore size. Chemical and mineralogical compositions of the colloid particles were determined by X-ray photoelectron spectroscopy in combination with ion etching of the particle surfaces. The host rocks were studied using characteristic samples from the surface outcrop nearest to the observation well. The analysis showed that the colloid particles consisted of an inorganic core with a discontinuous organic cover. The inorganic core was close in composition to the host rocks along the flow path with a predominance of layered hydrosilicates.