A green and facile electrochemical approach to synthesize novel cadmium/aluminum layered double hydroxides on a glassy carbon electrode (Cd/Al-LDHs/GCE) was proposed. The morphology and structure of Cd/Al-LDHs were characterized by scanning electron microscopy, energy dispersive spectrometer, powder X-ray diffraction. The results indicated that Cd/Al-LDHs were successfully prepared. Cyclic voltammetry and electrochemical impedance spectroscopy were employed to investigate the electrochemical behaviors of Cd/Al-LDHs/GCE. The Cd/Al-LDHs was served as an electrochemical probe in the detection of anthracene. And the Cd/Al-LDHs electrochemical response was greatly suppressed in presence of anthracene. A sensitive and convenient electrochemical method was developed for the determination of anthracene. The linear range and detection limit were 0.1-100.0 pM and 0.5 fM respectively. The method was successfully applied to determine anthracene in cloud-rain water samples of Mount-Taishan. This work provides a promising strategy for polycyclic aromatic hydrocarbons analysis at a very low concentration.