A new method for the separation and enrichment of actinides based on the use of polymer reagents is presented. In this study, poly(ethyleneimine methylphosphonic acid) was used for the interaction with actinide ions in the homogeneous phase. In conjunction with membrane filtration this reagent allows both the separation and the enrichment of actinides from dilute solutions. The retention profiles for the series of actinides U(VI), Np(V), Pu(IV), Am(III), Cm(III), Cf(III) were investigated at different pH. Retention differences between 0% and 100% were found depending on the actinide element and pH. Thus, these elements can be separated and enriched form aqueous solutions of binary or multi-component mixtures.