During the course of our recent work performed to develop an electroplated CoNiFe ternary alloy with high saturation magnetic flux density and low coercivity for use in magnetic recording heads, it was observed that two common sulfur-containing additives, saccharin and thiourea, behave differently with respect to the dependence of sulfur inclusion and coercivity of the alloy film on the additive concentration in the plating bath. To understand the cause of this difference, scanning tunneling microscopy (STM) was performed, using Au(111) as the substrate, to examine the structure of the adsorbed layers of the additive molecules. The result revealed that the nature of adsorption is fundamentally different for the two different additives; i.e., the adsorption of saccharin is physical and reversible, whereas thiourea undergoes irreversible chemisorption. This finding is consistent with the known behaviors of the two additives in the electroplating of nickel. In this paper the different effects of saccharin and thiourea in the electrodeposition of CoNiFe alloy are interpreted based on the STM results and relevant information available in the literature on the electrodeposition of nickel.