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Abstract Materials in crystalline form possess translational symmetry (TS) when the unit cell is repeated in real space with long‐ and short‐range orders. The periodic potential in the crystal regulates the electron wave function and results in unique band structures, which further define the physical properties of the materials. Amorphous materials lack TS due to the randomization of distances and arrangements between atoms, causing the electron wave function to lack a well‐defined momentum. High entropy materials provide another way to break the TS by randomizing the potential strength at periodic atomic sites. The local elemental distribution has a great impact on physical properties in high entropy materials. It is critical to distinguish elements at the sub‐nanometer scale to uncover the correlations between the elemental distribution and the material properties. Here, the use of synchrotron X‐ray scanning tunneling microscopy (SX‐STM) with sub‐nm scale resolution in identifying elements on a high entropy alloy (HEA) surface is demonstrated. By examining the elementally sensitive X‐ray absorption spectra with an STM tip to enhance the spatial resolution, the elemental distribution on an HEA's surface at a sub‐nm scale is extracted. These results open a pathway towards quantitatively understanding high entropy materials and their material properties.