Plants take up cadmium (Cd) from the soil, and the concentration of Cd in some plant products is a health concern. Plant uptake of Cd is poorly predicted by its concentration in soils; consequently, there is interest in the binding and distribution of Cd in soil. Synchrotron micro-X-ray fluorescence spectroscopy (micro-XRFS) is the most sensitive method of observing this distribution. We used beam-line 2-ID-D of the Advanced Photon Source (APS), Argonne, to test whether this technique could map the Cd distribution in 5 soils from Greater Sydney that contained 0.3–6.4 mg Cd/kg. A subsample of one soil was spiked to contain ~100 mg Cd/kg. Cadmium was readily mapped in the Cd-enriched subsample, whereas in the unamended soils, only one Cd-rich particle was found; that is, sensitivity generally limited Cd mapping. We also examined a sample of Nauru phosphorite, which was a primary source of much of the Cd in farm soils on the peri-urban fringe of Greater Sydney. The phosphorite contained ~100 mg Cd/kg and the Cd was relatively uniformly distributed, supporting the findings of an earlier study on an apatite from Africa. The micro-XRFS at beam-line 2-ID-D of the APS can be reconfigured to increase the sensitivity at least 10-fold, which may allow the distribution of Cd and its elemental associations to be mapped in particles of most agricultural soils and facilitate other spectroscopic investigations.