Abstract-A new efficient route for the synthesis of a cyclic monomer of perdeuterated poly(ethylmethylsiloxane) (PEMS) is reported. The perdeuterated cyclotrisiloxane has been prepared for the first time in an eight-step reaction starting from fully deuterated methanol and ethanol. Chromatographic and spectroscopical methods indicate a high purity as well as almost total deuteration of the 2,4,6-tri(pentadeuteroethyl)-2,4,6-tri(trideuteromethyl)cyclotrisiloxane. All the reaction steps have been previously investigated by the similar preparation of the protonated 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane as a model for the synthesis of the corresponding perdeuterated monomer.