Polycarbonate diols (PCDLs) are known as important intermediates for the manufacture of novel polyurethanes. In this work, PCDLs were prepared via the reaction of hexane-1,6-diol (HD) and dimethyl carbonate (DMC) using calcined MgAl hydrotalcites (HTc) as solid base. The effects of preparative parameters of the catalysts and reaction conditions on the transesterification reaction were investigated. X-ray diffraction (XRD), thermogravimetric analysis-differential scanning calorimetry (TG-DSC), CO2 temperature-programmed desorption (CO2-TPD), and Brunauer-Emmett-Teller (BET) techniques were used to characterize the HTc. The experimental results showed that the pore structure of the catalysts played a crucial role for the synthesis of PCDLs with high efficiency.