Described are anion-exchange materials having extraordinarily high affinity for plutonium anions such as plutonium (IV), and technetium anions such as pertechnetate. Preferred inventive resins are highly divinylbenzene cross-linked polyvinylpyridine resins exhibiting a macroreticular bead form, which have been quaternized to contain a substantial amount of 1-alkyl-pyridinium groups wherein the alkyl group has 4 to 8 carbon atoms. The inventive resins can be used in preferred processes for recovering plutonium and/or technetium anions from aqueous mediums, for example nuclear waste streams or groundwater related to civilian or defense-related nuclear operations.