We studied the effect of annealing on magneto-transport, magnetic, and structural properties of Cu100−x Co x (x = 5, 10, 20) glass-coated microwires prepared using the Taylor-Ulitovsky technique. Both as-prepared and annealed samples exhibit magnetoresistance effect. We observed a Kondo-like effect in as-prepared and annealed Cu95Co5 microwire and a significant increase of the giant magnetoresistance (GMR) in all studied Co-Cu after annealing. The origin of GMR effect and Kondo-like behavior is discussed considering structural changes of the annealed samples.