The nanospheres and nanofibers of CdS were prepared by simple chemical precipitation method using a mixture of water:butanol:ethylenediamine solvents. The effect of either water or butanol as solvents and the volume ratio of butanol:ethylenediamine on the morphology, crystallinity, electronic and surface properties of CdS were investigated. The obtained CdS nanospheres or nanofibers were analyzed by X-ray diffraction, field emission scanning electron microscopy and diffuse reflectance spectroscopy. An evolution from nanospheres to nanofibers depending on the relative fraction of solvent and chemical species was observed, which was driven by the formation of Cd-complexes and S-polymerized precursors. The chemical composition and surface properties of CdS nanostructures as function of the butanol:ethylenediamine solvent ratio used for the synthesis were analyzed by X-ray photoelectron and infrared spectroscopies. The correlations between the morphology, crystallinity, electronic and surface properties with the photocatalytic activity of CdS was investigated in the bluephoto-assisted reduction of 4-Nitrophenol using hydrazine as sacrificial electron donors (SED ' s). The impact the others SED's in the presence of citric acid on the increasing of photoactivity of CdS as function of created shallow energetic states was investigated by photoelectrochemical characterization.