During recent decades, mining and hydraulic fracturing activities have contributed to the release of 226Ra in the environment, one of the most radiotoxic natural radionuclides because of its similarity to calcium. Current issues are nowadays related to the understanding of its geochemical behavior and its transport mechanisms in the environment which implies being able to precisely measure Ra at ultra-trace level in complex matrices. A sample pretreatment step is therefore essential before analysis, independently of the measurement technique selected. Among the commercial resins, rare succeed alone to selectively extract Ra2+ from the other alkali or alkaline-earth cations that are much more concentrated in the samples, and most extraction procedures are complex and involved multi-steps. Much attention has been drawn on grafting well-designed macrocyclic ligands on resins but this solution implies synthesizing complex molecules of significant cost and the grafting procedure can affect their binding properties. In this study, we investigated for the very first time the potential of ion imprinted polymers (IIPs) to selectively extract Ra2+. Synthesized in the presence of the targeted ion or an analogous ion (Ba2+ in our case) forming a complex with one or several kinds of monomers, IIPs possess specific cavities enabling the recognition of the targeted ion. Complexation studies by mass spectrometry were first implemented to identify the best monomer candidates among the following four ones alone or in mixture (di(ethylene glycol) divinyl ether, methacrylic acid, 2-vinylpyridine, and vinylphosphonic acid), and the template/monomers ratios. The solubility of the retained polymerization mixtures was evaluated in 7 porogens and conductimetry experiments were finally conducted to determine the required complexation time in the selected porogen. From this screening approach, 5 Ba(II)-IIPs were synthesized by bulk polymerization using Ba(NO3)2, divinylbenzene, and acetonitrile/dimethylsulfoxyde, as template, crosslinker, and porogen, respectively. As a comparative support, a non-imprinted polymer (NIP) was synthesized for each IIP under the same conditions, but without template ion. Performances of all supports in solid phase extraction (SPE) were evaluated by analyzing the resulting extracted fractions by inductively coupled plasma mass spectrometry (ICP-MS). The vinylphosphonic acid-based IIP appeared to be the most promising during characterizations, enabling the separation of radium from alkalis and other metals (V, Mo, W, As, Sb, etc.). A gain in specificity was obtained by varying the template/monomers proportion, and the repeatability of the synthesis was also evaluated. After optimization of the SPE procedure and measurement of capacities and breakthrough volumes, the best IIP support was selected for an application to mineral water samples and for comparison with commercial resins.