Magnetism, XRD, and EXAFS analyses were used to study the formation of a solid solution on Pd-Co/G catalysts during reduction treatment. After reduction at 773 K, magnetic measurements revealed the formation of a Pd-Co alloy. XRD analysis in situ allowed us to follow the alloy process during the increase of the reduction temperature. The XRD results showed the presence of a heterogeneous solid solution after reduction at 773 K. Pd and Co K-edge EXAFS analysis confirmed that bimetallic particles with a palladium- and cobalt-rich phase were formed. The formation of a solid solution decreased the adsorption strength of 1,3-butadiene on new Pd sites modified by Co.