The reduction of a Re promoted Co/γ-Al2O3 catalyst was monitored in situ by synchrotron X-ray powder diffraction (XRPD) under H2 environment. Whole powder pattern analysis revealed a non-linear expansion of the unit cell of γ-Al2O3 during the reduction process, suggesting the diffusion of Co cations into the structure of the support. The non-linear cell expansion coincided with the formation of a CoO phase. In addition, space resolved diffraction at the inlet and the outlet of the reactor evidenced a negative effect of the partial pressure of indigenous H2O(g) on the reduction process.