A surface alloying technique was investigated using asymmetric alternating pulsed electrolysis in an aqueous solution containing a single metal component for the formation of an Fe-Cr layer on an iron substrate. In the process, the iron substrate was dissolved during each anodic polarization of the pulsed electrolysis, providing iron ions in the vicinity of the substrate, while the Fe-Cr alloy was electrodeposited during subsequent cathodic polarizations. A bright, flat, and crack-free Fe-Cr layer with a composition gradient was obtained using a solution containing a trivalent chromium component and a complex forming agent together with some supporting or buffering salts. (c) 2006 The Electrochemical Society.