A facile and highly sensitive electrochemical sensor for salidroside was fabricated based on multilayer ultrathin films (UTFs) containing Ni-Al layered double hydroxide (LDH) and carbon fibers that obtained by electrospinning technology. The X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) images show that the film surface is synthesized successfully. In addition, we constructed the electrochemical sensor using the composite nanomaterials we prepared to achieve detection of salidroside and this sensor showed a good linear range (0.2-120 mu M) and a low detection limit (0.067 mu M). It has also been successfully applied to the detection of actual samples, compared with HPLC method, satisfactory recovery rates have also been obtained.