The invention discloses a synthetic method of emtricitabine intermediates, namely, (2R, 5S)-5-(5'-fluoro-cytimidine-1-group)-1, 3-oxathiolane-2-carboxylic acid-L-menthyl ester having the structural formula of (VI), (2R, 5S)-5-hydroxy-1, 3-oxathiolane-2-carboxylic acid-L-menthyl ester having the structural formula of (III) is taken as raw material to obtain chloro compounds having the structural formula of (IV) by chlorination reaction, then the chloro compounds (IV) are treated with condensation and hydrolyzation reactions with N, O-bis(trimethoxy)5-flurocytosin having the structural formula of (V), thus obtaining the (2R, 5S)-5-(5'-fluoro-cytimidine-1-group)-1, 3-oxathiolane-2-carboxylic acid-L-menthyl ester (VI). The invention uses bis(trichloromethyl) carbonic ester to replace the thionyl chloride in the prior art so as to be taken as a chlorination reagent, thus having the advantages of safe and reliable operation and environmental protection.