A detailed study of the valence state and distribution of the AuCl3/AC catalyst during the acetylene hydrochlorination deactivation process is described and discussed. Temperature-programmed reduction and X-ray photoelectron spectral analysis indicate that the active Au(3+) reduction to metallic Au(0) is one reason for the deactivation of AuCl3/AC catalyst. Transmission electron microscopy characterization demonstrated that the particle size of Au nano-particles increases with increasing reaction time. The results indicated that metallic Au(0) exhibits considerable catalytic activity and that Au nano-particle aggregation may be another reason for the AuCl3/AC catalytic activity in acetylene hydrochlorination.