The reaction of 2-acetylthiophene with thiosemicarbazide and 4-phenylthiosemicarbazide yielded 2-acetylthiophene thiosemicarbazone (1) and 2-acetylthiophene 4-phenylthiosemicarbazone (2). Both compounds were fully characterised by 1H and 13C{1H}-NMR and infrared spectroscopies and showed satisfactory elemental analysis. The X-ray crystallographic studies can be summarised as follows: (1) triclinic, P-1, a=5.6515(3), b=10.1401(6), α=105.4260(10)°, β=94.202(2)° and γ=90.234(2)°, and Z=2; (2) triclinic, P-1, a=9.0352(4), b=9.7898(4), α=104.6820(10)°, β=102.8180(10)° and γ=108.28(10)°, and Z=4.