A mesoporous Al-doped silica (Al/SiO 2) was synthesised according to the published method, and then used to modify the carbon paste electrode (CPE). The electrochemical behaviour of catechol was investigated. Compared with the unmodified CPE, the resulting mesoporous Al/SiO 2 modified CPE remarkably increases the peak currents of catechol, and greatly lowers the peak potential separation. Therefore, the mesoporous Al/SiO 2 exhibits catalytic activity to catechol and significantly improves the determining sensitivity. Based on this, a sensitive, rapid and convenient electrochemical method was proposed for the determination of catechol. The linear range is between 5.0 × 10 −7 and 5.0 × 10 −5 mol L −1 with a correlation coefficient of 0.998. The limit of detection is as low as 1.0 × 10 −7 mol L −1. Finally, this novel method was employed to determine catechol in tea samples, which testified by high-performance liquid chromatography.