SUMMARYA cold zinc phosphating bath was formulated and optimized to study the effect of some cationic surfactants viz., Dodecylamine (DDA), Tetradecylamine (TDA), Hexadecylamine (HDA) and Octadecylamine (OCA) on the growth and the crystal habit of zinc phosphate coating on mild steel. Studies have been carried out regarding the mode of adsorption and how these additives modify the crystallization kinetics. The properties of the coated layer and corrosion performance were also investigated to correlate with the effect of surfactants. The study concludes that the addition of these cationic surfactants decreases the coating weight, lengthens the induction period and decreases the rate of crystallization following their adsorption as onium cations. This leads to the formation of fine-grained coatings with improved physical properties and corrosion performance.