The paper presents experimental results concerning the structural-phase state, diffusion processes and magnetoresistive properties of three-layer films Сo(1 -x)Crx/Cu/Co/substrate (S) with Cr concentration in the upper layer up to 30 at. %. It is shown that the phase composition of both as-deposited and thermostabilized at the temperature of 700 K film samples with the layer thickness of 1÷30 nm corresponds to α(Co), f.c.c.(Cu) and α(Сo1 -xCrx). Studies of diffusion processes have shown that in the systems Сo(1 -x )Crx/Cu/Co/S the individuality of the layers is largely preserved both in the as-deposited state and after annealing at Tа 700 K with the penetration of Cr atoms through the Cu layer. It was found that for as-deposited and annealed at temperatures of 400 and 550 K films Сo(1 -x)Crx/Cu/Co/S with cCr 30 at. % in the upper layer, dF 20÷30 nm and dN 3÷15 nm there is an atypical character of the behavior of the field dependences of the magnetoresistance is due to the different values of the spin asymmetry coefficients of the ferromagnetic layers α