The single X-ray structures of the thiosemicarbazide complexes [Cd(NH 2 CSNHNH 2 )Cl 2 ] n ·H 2 O (A) and [Cd(NH 2 CSNHNH 2 ) 2 Cl 2 ] n (B) are reported. Both compounds have been found to be effective as single source precursors for the preparation of CdS nanomaterials. Thermal decomposition of the precursors in hexadecylamine (HDA) results in the formation of nanorods of different dimensions. The powder X-ray diffraction patterns of the nanodimensional materials reveal differences in the phases of the CdS synthesized from the two complexes. The particles synthesized from both precursors show quantum confinement effects in their absorption spectra, with the evidence of a broad defect emission in their photoluminescence spectra.