Greenockite (CdS) nanostructured thin films are deposited on soda and FTO conducting glass substrates by aerosol‐assisted (AA)CVD using a single‐source precursor bis‐(N,N‐dicylcohexyldithiocarbamato)(pyridine)cadmium(II), Cd[S₂CNCy₂]₂.py (1), in pyridine, toluene, and THF solutions in the temperature range 350–450 °C. The precursor 1, characterized by physicochemical methods, undergoes facile thermal decomposition at 350 °C to give a stable residual mass of CdS. The thin films deposited from pyridine solution, and characterized by X‐ray diffraction (XRD), UV‐vis spectroscopy, field‐emission scanning electron microscopy (FESEM), and energy dispersive X‐ray (EDX) techniques, exhibit a band gap of 2.4 eV and a photocurrent density of 1.3 mA cm⁻² at 0.4 V versus Ag/AgCl/3M KCl, suggesting their suitability for application in photoelectrochemical (PEC) cells.