2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) is a highly toxic persistent organic pollutant (POP) that can remain present in the environment for a long time. Prolonged exposure to TCDD may bring about a wide variety of deleterious health effects to humans. Based on these circumstances, a rapid and facile surface-enhanced Raman scattering (SERS) method with gold nanoparticle-modified silver nanorod (AuNP@AgNR) substrates was developed for detection of 2,3,7,8-TCDD. Compared with SERS-active gold nanoparticles and silver nanorod substrate, the prepared AuNP@AgNR substrate showed an outstanding SERS performance with an enhancement factor of up to 2.4 x 10(8). Furthermore, using AuNP@AgNR as a SERS substrate, we achieved the highly sensitive detection of 2,3,7,8-TCDD, and a density functional theory calculation was 6 to assign the characteristic peaks of 2,3,7,8-TCDD. The reliable linear range was determined to be 10 ng mL(-1) to 10 mu g mL(-1), with the limit of detection and the limit of quantitation as low as 7.1 and 8.2 ng mL(-1), respectively. By this method, the recovery rates of 2,3,7,8-TCDD spiked in the river samples were 82.3-97.4% with a relative standard deviation between 1.9 and 8.4%. These results show that the AuNP@AgNR substrate can be used for highly sensitive detection of 2,3,7,8-TCDD and has potential applications in the detection of other POPs.