A catalyst for the preparation of dimethyl carbonate from urea and methanol having a composition on weight base of: active component of from 20 to 50 wt %, and carrier of from 80 to 50 wt %, and prepared by equal-volume spraying and impregnating method is disclosed. The method for the synthesis of dimethyl carbonate can be carried out in a catalytic rectification reactor, said method comprising: (1) dissolving urea in methanol to form a methanol solution of urea; and (2) feeding the methanol solution of urea and methanol counter-currently into the reaction zone, wherein the reaction is carried out at conditions including reaction temperature of from 120° C. to 250° C., reaction pressure of from 0.1 MPa to 5 MPa, kettle bottom temperature of from 70° C. to 210° C., stripping section temperature of from 70° C. to 250° C., rectifying section temperature of from 70° C. to 280° C., and reflux ratio of from 1:1 to 20:1. The preparation of the catalyst according to the present invention is simple and has good repeatability, and the catalyst could further enhance the yield of DMC as well as conversion of urea in the catalytic rectification reactor.