To improve the sulfuric-acid leaching of germanium-bearing secondary zinc oxide, the occurrence states and sulfuric-acid leaching behavior of germanium in secondary zinc oxide were investigated experimentally via inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray diffraction (XRD), scanning electron microscopy and energy-dispersive spectroscopy (SEM-EDS), electron probe microanalysis (EPMA), and chemical phase analysis combined with leaching tests. The germanium-bearing secondary zinc oxide was produced via a fuming process of lead smelting slag and zinc leaching residue in a lead and zinc smelter. The results show that zincite, wurtzite, galena, and anglesite are the major minerals containing zinc and lead in the secondary zinc oxide. Further, these zinc- and lead-bearing materials contain germanium (without independent minerals). In the sulfuric-acid leaching process without oxidant, wurtzite and galena cannot be leached, which results in a loss of germanium. Anglesite, which exists originally in the secondary zinc oxide or was formed in the leaching process, contains a low amount of germanium and exhibits a loss of germanium in the residue. Moreover, the leaching efficiencies of germanium and zinc increased to 99.7% and 99.4% in the leaching process under oxygen pressure, respectively.