Most Zr conversion coatings are prepared on Al alloys, with Al3+ from the substrate contributing significantly to the film growth process. Thus, the effect of Al3+ on the electrochemical characteristics, surface microstructure and film-formation mechanism of Zr-based conversion coatings on old- rolled steel (CRS) substrates was investigated by growing the coatings with and without Al3+ as an additive. Electrochemical tests indicated that the anticorrosion performance of the Zr-Al coatings prepared in the presence of Al3+ was greatly superior to that of Zr conversion coatings obtained in the absence of Al3+. Field-emission scanning electron microscopy and X-ray photoelectron spectroscopy analysis indicated that adding of Al3+ in the conversion bath changed the surface microstructure of the Zr coating, greatly promoted the deposition of Zr and F on the CRS substrate and increased the film thickness and density. Both coatings were embedded into the etched CRS substrates. The presence of Al3+ additive induced the formation of different coating components. The Zr coating mainly consisted of ZrO2 and some FeFx, whereas the Zr-Al coatings comprised of ZrO2, ZrOxFy, Al2O3, AlFx and some FeFx. The present study results confirm the key role of Al3+ as an additive in the film formation and growth process of Zr coatings and its effect on enhancing the anticorrosion performance of CRS substrates in NaCl solutions.