Implementing a newly developed spectrometer for the soft x‐ray range of (35–130) eV based on reflection zone plates was successfully accomplished on an electron probe microanalyzer. In this context, we present the first spectra acquired using this setup, including those of elements such as Be (Kα), C (Kα), Mg (L2,3), Al (L2,3), and Si (L2,3). We have also conducted an analysis of several lithium compounds and measured the emission of Li Kα from metallic Li, LiF, and LiNbO3. Some of the results were compared with density functional theory calculations. The spectrum obtained for the lithium‐bearing mineral amblygonite Li0.75Na0.25Al(PO4)F0.75(OH)0.25 is chosen to discuss some of the challenges faced.