•Highly-sensitive analytical method was developed for ponceau 4R and tartrazine.•Porous alumina microfibers were prepared and used to enhance the sensitivity greatly.•It was demonstrated with drink samples, and the accuracy was tested by HPLC.Alumina microfibers were prepared and used to construct an electrochemical sensor for simultaneous detection of ponceau 4R and tartrazine. In pH 3.6 acetate buffer, two oxidation waves at 0.67 and 1.01 V were observed. Due to porous structures and large surface area, alumina microfibers exhibited high accumulation efficiency to ponceau 4R and tartrazine, and increased their oxidation signals remarkably. The oxidation mechanisms were studied, and their oxidation reaction involved one electron and one proton. The influences of pH value, amount of alumina microfibers and accumulation time were examined. As a result, a highly-sensitive, rapid and simple electrochemical method was newly developed for simultaneous detection of ponceau 4R and tartrazine. The detection limits were 0.8 and 2.0 nM for ponceau 4R and tartrazine. This new sensor was used in different drink samples, and the results consisted with the values that obtained by high-performance liquid chromatography.