An original experimental procedure is set up in order to relate unambi
guously the equilibrium impurity segregation in a grain boundary to th
e structural modifications. This is clearly established in the case of
the Ge(S) Sigma = 25 grain boundary. Using HREM, EDS and EELS, we sho
w that the sulfur segregation occurs on the dislocation cores of the g
rain boundary and that it stabilizes the lowest energy structures of t
he initial one.