The effective accumulation and the rapid trace detection of sulfadiazine, amikacin, enrofloxacin and ciprofloxacin are realized by the hyphenated technology of surface enhanced Raman spectroscopy (SERS) and electrostatic preconcentration (EP). The experimental results show that, if compared with those by the non-EP-SERS detection, the characteristic peak intensities of sulfadiazine and amikacin are increased by about 10 times, and the characteristic peak intensities of enrofloxacin and ciprofloxacin are increased by 2-3 times. The minimum detectable concentrations of the 4 kinds of antibiotics are 1.9×10-8, 1.7×10-8, 5.5×10-8 and 6.0×10-8 mol·L-1, respectively. A good linear relationship between the characteristic peak intensity and detection concentration appears when the concentration of detected targets is relatively low. The detection sensitivity of antibiotics in aqueous can be improved effectively by using the EP-SERS technology.