Saliva, an easily accessible biofluid, is validated as biomarker of arsenic (As) exposure in several villages of West Bengal, India. Pentavalent arsenic [As(V)] was found to be the predominant species in saliva, with the amount of inorganic As [As(V) and trivalent form, As(III)] being more than half of the total As in the samples. Significant association was found between total daily ingestion of As and As(V) (r = 0.59; p = 0.000), As(III) (r = 0.60; p = 0.000), dimethylarsinous acid (DMA(V)) (r = 0.40; p = 0.000), and monomethylarsonous acid (MMA(V)) (r = 0.44; p = 0.000), implying that these species have mainly been derived from the methylation of the inorganic As in the water that study participants drank and the food they ate. Analysis of confounding effects of age, sex, smoking, body mass index and the prevalence of skin lesion suggests that women and controls with no skin lesion had a higher capacity to methylate the ingested As compared to the rest of the population. Thus, our study demonstrates that As species in saliva can be an useful tool to predict the individual susceptibility where higher As exposure and a lower methylation capacity are implicated in the development of As-induced health effects.