The development of highly efficient alkaline catalysts with abundant base sites is of paramount importance for the synthesis of polycarbonate diols (PCDLs). And the application of heterogeneous catalysts is an effective strategy to address the effect of residual catalysts on the quality of PCDLs. Here, Ce cooperated layered double oxide (LDO-Ce) was used as a catalyst for the preparation of PCDLs via transesterification between dimethyl carbonate (DMC) and 1,4-butanediol (BDO). CO₂ temperature-programmed desorption (CO₂-TPD) profiles demonstrated that the introduction of Ce led to an increase in strong base sites of LDO-Ce, thus endowing LDO-Ce with excellent catalytic performance. Besides, LDO-Ce possessed satisfactory specific surface area and pore size. A possible catalytic mechanism was proposed to illustrate the transesterification process. The effects of the reaction conditions on the hydroxyl value, yield, and BDO conversion were further investigated in detail. The yield of PCDLs with a hydroxyl value of 112.2 mg KOH/g (corresponding to a number average molecular weight [M_n] of 1000 g/mol) was 92.44% under its optimum reaction conditions (w (catalyst) = 0.5%, n(DMC)/n(BDO) = 1.25, T-_{transesterification} = 130°C, t-_{transesterification} = 5 h, T-_{polycondensation} = 170°C, t-_{polycondensation} = 4 h, P-_{polycondensation} = 10 kPa). Moreover, LDO-Ce was easily removed after the transesterification process (Step 1), ensuring the quality of PCDLs, and it was recycled three times without significant loss of catalytic activity.