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Substitution of zinc chromate or zinc yellow, traditionally used as anticorrosive pigment, for other phosphate‐based pigments that are not hazardous to health and have the same anticorrosive behaviour or even better, is studied in this paper. Four alkyd paints were specially prepared; two of them contained calcium acid phosphate or micronised zinc phosphate as anticorrosive pigments respectively. A paint containing zinc chromate was used as reference and a paint without anticorrosive pigments was used as a blank, in which the other ingredients were increased proportionally to attain the desired PVC relationship. The corrosion behaviour of low carbon steel panels coated with these paints in a 3 per cent NaCl solution was assessed by electrochemical impedance spectroscopy (EIS). In addition, other painted panels were evaluated by salt spray and humidity chamber tests. Results of all tests showed that the paint with calcium acid phosphate and especially that with micronised zinc phosphate exhibited better behaviour than paint with zinc chromate. Analysis of impedance parameters (ionic resistance and capacitance of the paint film) against immersion time allowed the paints to be ranked in the same order as that obtained with salt spray and humidity chamber tests.