Solid‐state sodium ion conductors are crucial for the next generation of all‐solid‐state sodium batteries with high capacity, low cost, and improved safety. Sodium closo‐carbadodecaborate (NaCB ₁₁ H ₁₂ ) is an attractive Na‐ion conductor owing to its high thermal, electrochemical, and interfacial stability. Mechanical milling has recently been shown to increase conductivity by five orders of magnitude at room temperature, making it appealing for application in all‐solid‐state sodium batteries. Intriguingly, milling longer than 2 h led to a significant decrease in conductivity. In this study, X‐ray Raman scattering (XRS) spectroscopy is used to probe the origin of the anomalous impact of mechanical treatment on the ionic conductivity of NaCB ₁₁ H ₁₂ . The B, C, and Na K‐edge XRS spectra are successfully measured for the first time, and ab initio calculations are employed to interpret the results. The experimental and computational results reveal that the decrease in ionic conductivity upon prolonged milling is due to the increased proximity of Na to the CB ₁₁ H ₁₂ cage, caused by severe distortion of the long‐range structure. Overall, this work demonstrates how the XRS technique, allowing investigation of low Z elements such as C and B in the bulk, can be used to acquire valuable information on the electronic structure of solid electrolytes and battery materials in general.