The effective use of alloying elements in powder metallurgical steels requires a deep understanding of their redistribution kinetics during sintering. In this work, interrupted sintering trials of Fe–2Cu and Fe–2Cu–0·5C compacts were performed. Moreover, diffusion simulations of Cu in γ-Fe using Dictra were performed. It is found that transient liquid phase penetrates the Fe interparticle and grain boundaries in less than 3 min of holding time. However, C addition limits the penetration of liquid Cu, particularly into grain boundaries of large Fe particles. The results also show that the mean diffusion distance of Cu in γ-Fe in the C added system is slightly lower than that in the C-free system at 3 min of holding time; however, after 33 min, the mean diffusion distance is similar in both systems. The diffusion distances of Cu in γ-Fe, predicted by Dictra, are in good agreement with the measured values.