A stable dihydroxybenzene sensor was fabricated by electrochemical deposition of Zn/Al layered double hydroxide film on glassy carbon electrode (LDHf/GCE). The sensitive and facile electrochemical method for the simultaneous determination of catechol (CA) and hydroquinone (HQ) under coexistence of resorcinol (RE) has been achieved at the LDHf/GCE in phosphate buffer solution (pH 6.5). Under the optimized conditions, the differential pulse voltammetry response of the modified electrode to CA (or HQ) shows a linear concentration range of 0.6 mM to 6.0 mM (or 3.2 mM to 2.4 mM) with a correlation coefficient of 0.9987 (or 0.9992) and the calculated limit of detection is 0.1 mM (or 1.0 mM) at a signal-to-noise ratio of 3. In the presence of 50 mM isomer, the linear concentration ranges for CA and HQ are 3.0 mM to 1.5 mM and 12.0 mM to 0.8 mM, respectively. The detection limits are 1.2 mM and 9.0 mM. Further, the proposed method has been performed to successfully detect dihydroxybenzene isomers in analysis of real samples, such as water and tea.