A set of mono- and bimetallic (Zn-Co) supported ZSM-5 catalysts was first prepared by PEG-additive method. The physicochemical properties of the catalysts were investigated by FTIR, XPS, XRD, N2 adsorption-desorption measurements, SEM, EDS and NH3-TPD techniques. The physicochemical properties showed that the ZnCo2O4 spinet oxide was formed on the ZSM-5 support and provided effectual synergetic effect between Zn and Co species for the bimetallic catalyst. Furthermore, bimetallic supported ZSM-5 catalyst exhibited weak, moderate and strong acidic sites, while the monometallic supported ZSM-5 catalyst showed only weak and moderate or strong acidic sites. Their catalytic performances for thermal decomposition of hexamethylene-1,6-dicarbamate (HDC) to hexamethylene1,6-diisocyanate (HDI) were then studied. It was found that the bimetallic supported ZSM-5 catalysts, especially Zn-2Co/ZSM-5 catalyst showed excellent catalytic performance due to the good synergetic effect between Co and Zn species, which provided a suitable contribution of acidic sites. HDC conversion of 100% with HDI selectivity of 91.2% and by-products selectivity of 1.3% could be achieved within short reaction time of 2.5 h over Zn-2Co/ZSM-5 catalyst. (C) 2017 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.