Post-Variscan vein-type Co-Ni-Bi ores of the Bieber deposit, Spessart mountains, Germany, which are related to the Permian Kupferschiefer, have been investigated by ore microscopy, X-ray powder diffraction and electron-probe microanalysis. The samples contain a variety of ore minerals, notably skutterudite, native bismuth, cobaltite, alloclasite, niccolite, maucherite, gersdorffite, rammelsbergite/pararammelsbergite, safflorite, loellingite and emplectite. The ores display structures indicative of multiple brecciation and complex zoned arsenide assemblages. Three sequential stages of deposition are identified, which are (1) the Cu stage, (2) the main Co-Ni-Bi stage, and (3) the late stage. The arsenide minerals, notably skutterudite, diarsenides and sulpharsenides, show a large range of compositional variation in Co-Ni-Fe space. A relatively limited number of skutterudite and diarsenide compositions lie outside the compositional fields established in the literature. Skutterudite and diarsenides are characterized by a significant substitution of As by S up to 0.44 a.p.f.u. and 0.31 a.p.f.u., respectively, which is larger than the range previously reported for these minerals. Sulpharsenide compositions can be grouped into three populations, which conform to cobaltian arsenopyrite, cobaltite and gersdorffite. They display highly variable As/S ratios between 0.95:1.00 and 1.29:0.73, consistent with experimental data. Estimates of the formation temperatures, based on the presence of dendritic native bismuth and emplectite, are in the range 100–300°C, similar to different post-Variscan mineralization styles widespread in Central Europe. Comparison of the Co-Ni-Bi vein assemblage with the framework of available paragenetic information and radiometric age data for regional mineralization events indicates an age of mineralization of ~150–160 Ma for the Bieber deposit.