A spectroelectrochemical setup has been developed to investigate radioactive elements in small volumes (0.7 to 2 ml) under oxidation–reduction (redox) con­trolled conditions by X-ray absorption spectroscopy (XAS). The cell design is presented together with in situ XAS measurements performed during neptunium redox reactions. Cycling experiments on the NpO$_2^{2+}$/NpO$_2^+$ redox couple were applied to qualify the cell electrodynamics using XANES measurements and its ability to probe modifications in the neptunyl hydration shell in a 1 mol l$^{-1}$ HNO$_3$ solution. The XAS results are in agreement with previous structural studies and the NpO$_2^{2+}$/NpO$_2^+$ standard potential, determined using Nernst methods, is consistent with measurements based on other techniques. Subsequently, the NpO$_2^+$, NpO$_2^{2+}$ and Np$^{4+}$ ion structures in solution were stabilized and measured using EXAFS. The resulting fit parameters are again compared with other results from the literature and with theoretical models in order to evaluate how this spectroelectrochemistry experiment succeeds or fails to stabilize the oxidation states of actinides. The experiment succeeded in: (i) implementing a robust and safe XAS device to investigate unstable radioactive species, (ii) evaluate in a reproducible manner the NpO$_2^{2+}$/NpO$_2^+$ standard potential under dilute conditions and (iii) clarify mechanistic aspects of the actinyl hydration sphere in solution. In contrast, a detailed comparison of EXAFS fit parameters shows that this method is less appropriate than the majority of the previously reported chemical methods for the stabilization of the Np4$^{4+}$ ion.