Polycarbonate diols (PCDLs) are known as important intermediate for the manufacture of novel polyurethanes. In this work, a series of KF loaded oxides and alumina doped with potassium halides were prepared and employed as the catalysts for the PCDL synthesis via the reaction of hextane-1, 6-diols (HD) and dimethyl carbonate (DMC) followed by vacuum oligomerization. Experimental results indicated that among the catalysts tested, KF/Al2O3 exhibited the best catalytic activity. Moreover, the catalyst could be reused for three times with acceptable catalytic activity. The basic centres with medium and strong strength generated through the interaction between KF and Al2O3 were catalytically active for the reaction.