New six unexpected 1,3,4-oxadiazoles were obtained starting from acylthiosemicarbazides. N1-[4-(4-X-phenylsulfonyl)benzoyl]-N4-(2/3-methoxyphenyl)-thiosemicarbazides 2,3a-c were treated with ethyl chloro- or bromoacetate in presence of anhydrous sodium acetate in order to obtain new thiazolidin-4-ones compounds. However, formation of desired thiazolidin-4-ones from these acylthiosemicarbazides failed and instead 1,3,4-oxadiazoles were obtained. For confirmation presence of these compounds, 5-[4-(phenylsulfonyl)phenyl]-2-(3-methoxyphenylamino)-1,3,4-oxadiazole 5a was synthetized by cyclodesulfurization of acylthiosemicarbazide 3a with mercury (II) acetate. The structures of these compounds were elucidated by FTIR, UV, 1H-NMR and 13C-NMR, MS spectra and elemental analysis.