Novel nano-silver coated multi-walled carbon nanotube composites were prepared and used to fabricate a modified electrode. The application of the nano-silver coated multi-walled carbon nanotube composites modified electrode for determination of trace thiocyanate is demonstrated for the first time. The influence of substrate, pH and interference of coexisting substances was investigated for response properties of the electrode. There was a linear relationship at the range 2.5 x 10(-9) to 5 x 10(-8) mol L(-1) and 5 x 10(-8) to 1 x 10(-6) mol L(-1) of thiocyanate with the decrement of anodic DPV peak currents. The limit of detection was 1 x 10(-9) mol L(-1)(S/N=3). The constructed electrode showed excellent reproducibility and stability. Actual urine and saliva samples of smoker and non-smoker were analyzed and satisfactory results were obtained. This method provides a new way to construct any electrode for biological and environmental analysis.