Perchlorate contamination was investigated in groundwater and surface water from Sivakasi and Madurai in the Tamil Nadu State of South India. Sensitive determination of perchlorate (LOQ = 0.005 μg/L) was achieved by large-volume (500 μL) injection ion chromatography coupled with tandem mass spectrometry. Concentrations of perchlorate were <0.005-7,690 μg/L in groundwater (n = 60), <0.005-30.2 μg/L in surface water (n = 11), and 0.063-0.393 μg/L in tap water (n = 3). Levels in groundwater were significantly higher in the fireworks factory area than in the other locations, indicating that the fireworks and safety match industries are principal sources of perchlorate pollution. This is the first study that reports the contamination status of perchlorate in this area and reveals firework manufacture to be the pollution source. Since perchlorate levels in 17 out of 57 groundwater samples from Sivakasi, and none from Madurai, exceeded the drinking water guideline level proposed by USEPA (15 μg/L), further investigation on human health is warranted.