It has been extensively investigated that smokeless tobacco chewing can lead mainly to inflammation of oral cavity. In present study, the total and artificial saliva extracted toxic elements, arsenic, cadmium, nickel and lead were estimated in smokeless tobacco product, mainpuri. Cloud point extraction has been used for the preconcentration of arsenic, cadmium, nickel and lead in artificial saliva extract, using complexing reagent, ammonium pyrrolidinedithiocarbamate. Total and extractable toxic elements were measured by electrothermal atomic absorption spectrometry. The chemical variables of cloud point extraction were optimized. The validity of methodology was tested by simultaneously analyzing certified reference material (Virginia tobacco leaves) and spike recovery test. The artificial saliva extractable levels of arsenic, cadmium, nickel and lead ranged from 15–22, 45–70, 35–58, and 18–32%, respectively, of total elemental contents in mainpuri samples. It was estimated that intake of 10g of different brands of mainpuri contributing the 5.88, 55.0, 45.0 and 40.3% of the provisional maximum tolerable daily intake for arsenic, cadmium, nickel and lead, respectively for adults of ~60kg.