We represent the results of a study on as the chelators used in the environmentally friendly electroless deposition bath changed depending on the amounts of hydroxides were present. The baths were prepared using polyhydroxides, glycerol and sorbitol, as chelators with copper methanesulfonate as the metal ion. Dimethylamine borane (DMAB) was used as the reducing agent withN-methylthiourea and cytosine, as additives in both the glycerol and sorbitol contained baths. Potassium hydroxide was used as the pH adjuster, with glycerol and sorbitol baths maintained at a pH of 11.50 and 10.75 respectively at a room temperature of 28 ± 2 °C. XRD, SEM, AFM, cyclic voltammetry studies, Tafel and Impedance studies, as well as additional methods, were employed to monitor and record the surface, structural, and electrochemical characteristics of the deposits and bath. The reports of the study gave interesting results, which clearly the effect of chelators on additives in the nano deposition of copper in an electroless deposition bath.