Display omitted •Development of radionuclide-selective solid-phase extraction (SPE) materials.•Operating mechanism of proprietary SPE products in radionuclide separation.•Application of proprietary SPE products for separation of radionuclides. Precise and rapid determination of radionuclides (RNs) in the environment is essential for environmental monitoring, radiological protection, and radioactive waste management due to the increasing use of nuclear energy globally, as well as the unprecedented release of RNs after nuclear accidents, e.g., Chornobyl, Fukushima. In this regard, sample preparation, which is an error-prone step in RN analysis, needs more attention to improve selectivity and sensitivity of analytical measurements by sample clean-up or pre-concentration. Solid-phase extraction (SPE) is an effective sample preparation technique capable of selectively separating target RNs from other matrix ions in environmental samples. Commercially available proprietary SPE products, packaged in columns, cartridges, or disk formats, have been widely used for sample purification in RN analysis. They have high affinity and selectivity for target RNs, and their reusability and ease of large-scale production make them more economical than other options. Since there have not been any reviews regarding selective separation of RNs using proprietary SPE products, this work reviews approaches that have been adopted for isolation of RNs (Cs, Sr, Tc, Th, U, Np, Pu, Am, and Cm) from environmental matrices. The review assumably provides information on selecting macro-SPE-assisted sample preparation techniques to separate and analyze RNs in environmental matrices.