Scanning transmission X-ray microscopy was used to investigate the speciation and spatial distribution of Co in a Co(II)-doped cement matrix. The aim of this study was to improve the understanding of the heavy metals immobilization process in cement on the molecular level. The Co-doped cement samples hydrated for 30 days with a Co loading of 5000 mg/kg were prepared under normal atmosphere to simulate conditions used for cement-stabilized waste packages. Co 2p(3/2) absorption edge signals were used to determine the spatial distributions of the metal species in the Co(II)-doped cement. The speciation of Co was determined by collecting near-edge X-ray absorption fine structure spectra. On the basis of the shape of the absorption spectra, it was found that Co(II) is partly oxidized to Co(III). The correlation, respectively the anticorrelation with elements such as Al, Si, and Mn, show that Co(II) is predominantly present as Co-hydroxide-like phase as well as Co-phyllosilicate, whereas Co(III) tends to be incorporated only into a CoOOH-like phase. Thus, this study suggests that thermodynamic calculations of Co(II)-immobilization by cementitious systems should take into consideration not only the solubility of Co(II)-hydroxides but also Co(III) phases.