Double leached Waelz oxide (DLWO), with 76% zinc, is a secondary zinc containing raw materials obtained by the treatment of electric arc furnace dust. The content of fluoride in DLWO is still too high for direct leaching, as fluoride has a detrimental effect on electrowinning for zinc production. Knowledge of the characteristics of DLWO, and especially on how a fluoride mineral might exist, can contribute to further improvement of the selective leaching for the removal of fluoride. In this study, DLWO was characterized using analytical techniques, such as inductively coupled plasma-optical emission spectroscopy (ICP-OES), F-19 liquid-state nuclear magnetic resonance (F-19 LS NMR), X-ray powder diffraction analysis (XRD), scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) and F-19 solid-state nuclear magnetic resonance (F-19 SS NMR). This study showed that DLWO mainly consisted of zincite (ZnO), cerussite (PbCO3) and a spinel containing zinc, iron and manganese. The fluoride mineral identified was calcium fluoride (CaF2). In SEM analysis, fluorine was found in larger grains together with calcium and oxygen, which was possibly calcium carbonate.