Cadmium(II) complexes of N,N′-diarylformamidine dithiocarbamate of the general formula [Cd-(L)2] (L = N,N'-bis(2,6-dimethylphenyl)formamidine dithiocarbamate L1 (1), N,N'-bis(2,6-disopropylphenyl)formamidine dithiocarbamate L2 (2), N'-(2,6-dichlorophenyl-N-(2,6-dimethylphenyl)formamidine dithiocarbamate L3 (3), N'-(2,6-dichlorophenyl)-N-(2,6-diisopropylphenyl)formamidine dithiocarbamate L4 (4) and their 2,2-bipyridine (bipy) adducts, [Cd-(L1)2bipy] (5), [Cd-(L2)2bipy] (6), [Cd-(L3)2bipy] (7), [Cd-(L4)2bipy] (8)) have been synthesized and characterized using various spectroscopic and analytical techniques. For one of the 2,2-bipyridine adducts, the molecular structure was determined using single crystal X-ray structure as a six-coordinate Cd(II) complex in which two pairs of sulfur atoms from two dithiocarbamate ligands and a pair of nitrogen atoms from bipy completed the distorted octahedral geometry. Complexes 1, 3 and 5 were used as single source precursors for formation of octadecylamine capped cadmium nanoparticles, CdS1, CdS3 and CdS5. HR-TEM images of as-synthesized CdS1, CdS3 and CdS5 particles are nano-spherical in shape with size distributions ranging between 4 and 9 nm. The as-synthesized CdS nanoparticles were used as photocatalysts for degradation of crystal violet, with degradation efficiency of 75-84% and rate constants of 0.0050, 0.0043 and 0.0039 min−1 for CdS1, CdS3 and CdS5, respectively.