The synthesis of three N-benzoyl-O-alkylthiocarbamates, particularly with ethyl, isobutyl and n-pentyl as alkyl group is reported in the present paper. The three compounds were investigated using NMR and IR techniques, as well as x-ray powder diffraction. IR spectral data show absorption bands of the NH (3208-3269 cm-1 y 1511-1526 cm-1), CO (1696-17805 cm-1), CS (1295-1361 cm-1) groups, and the aromatic ring. The absorption frequencies agree with those reported in previous references for similar compounds. The CO stretching frequency is greater than expected for a secondary amide, due to high electronic delocalization of the fragment [CO-NH-CS-O]. 1H-NMR spectral data show wide signals corresponding to chemical shifts for the proton of NH group (9.22-9.40 ppm), which are a result of the 14N electric cuadrupole effect on the proton. 13C-NMR spectra exhibit signals of CO (162-163 ppm) and CS (189 ppm) groups, which are the most deshielded ones of each spectrum. Thiocarbonilic carbon atom is more deshielded than the carbonilic one, due to the higher average excitation energy of the last one. X-ray diffraction patterns show sharp intensity maxima, which result from the high crystallinity of the three solid phases (low background and no amorphous zone). All patterns were indexed. The cell parameters were determined and refined. Crystals of N-benzoyl-O-ethylthiocarbamate are orthorhombic, a = 11.443 (5), b = 10.035 (4), c = 9.397 (5) Å, space group Pmmm. Crystals of N-benzoyl-O-isobutylthiocarbamate are monoclinic, a = 8.274 (2), b = 17.182 (3), c = 4.884 (1) Å; ? = 103.93 (4)º, space group P2/m. Crystals of N-benzoyl-O-n-pentylthiocarbamate are monoclinic, a = 8.427 (3), b = 18.055 (6), c = 6.649 (2) Å; ? = 109.23 (4)º, space group P2/m. The structures of these compounds agree with their IR, 1H-NMR and x-ray diffraction spectra.