Although the conventional methods for strong attachment of chitosan onto stainless steel require many steps in different solvents, it has been demonstrated in this work that covalent grafting of chitosan on a steel surface can be easily achieved through the formation of a self-adhesive surface based on aryldiazonium seed layers. Initially, a polyaminophenyl layer is grafted on a stainless steel surface by means of the one-step GraftFast(TM) process (diazonium induced anchoring process). The grafted aminophenyl groups are then converted to an aryldiazonium seed layer by simply dipping the substrate in a sodium nitrite acidic solution. That diazonium-rich grafted layer can be used as a self-adhesive surface for subsequent spontaneous coating of chitosan onto the steel surface. X-ray photoelectron and impedance electrochemical spectroscopies were used to characterize the pristine and modified steel samples. As evidenced from impedance and linear polarization results, the primary polyaminophenyl layer characterized by a high charge transfer resistance contributed to better protection against corrosion of the resulting chitosan-coated steel in sulfuric acid medium.