The following contribution shows the results of investigations on an influence of alkali metals compounds on physicochemical and catalytic properties as well as the most important operating parameters of Cu/ZnO/Al2O3 system, with a composition being similar to typical industrial heterogeneous catalysts for LT-WGS process. The addition of cesium or potassium to the Cu/ZnO/Al2O3 catalyst causes a decrease of copper surface. It gives remarkable inhibition of methanol synthesis, accompanying by a relatively small influence on the activity towards WGS. (C) 2011 Elsevier B.V. All rights reserved.