Metastable Co(x)Cu100-x(x=5, 10, 15, 20) alloys have been annealed at increasing temperatures in order to study the evolution of the Co cluster and its relation with the magnetotransport properties. The structure was investigated by X-ray Absorption Spectroscopy on the Co K-edge as a function of composition and annealing temperature. An anomalous trend in the structural evolution has been evidenced and related to the preculiar features observed in the magnetotransport properties.