A series of trimetallic Ru-Co(III)-Cu(II)/SAC catalysts were synthesized and assessed for acetylene hydrochlorination, combining with characterizations of TPR, TPD, TGA, TEM, XPS, EXAFS, etc. Compared with the monometallic and bimetallic catalysts, the trimetallic Ru1Co(III)3Cu(II)1/SAC catalyst with 0.1 wt% Ru loading shows a superior activity with the acetylene conversion of 99.0%. It is illustrated that co-addition of Co(III) and Cu(II) can make the ruthenium active species dispersed highly on the carrier, and Cu(II) species can not only inhibit the reduction of RuCl3 precursors, but also make Co2+ or Co degrees transform to high valent species of Co(III), resulting in more ruthenium oxides and low valent Cu+/Cu degrees species. The Ru1Co(III)3Cu(II)1/SAC is a promising non-mercuric catalyst for acetylene hydrochiorination reaction with the advantages of environmental benign and low cost. (C) 2016 Elsevier B.V. All rights reserved.