Chlorpyrifos is the most common organophosphate compound registered for agricultural use in Vietnam. The aim of this study was to evaluate chlorpyrifos exposure to rice farmers in Vietnam, using a probabilistic approach. Urine samples on a 24-h basis were collected from farmers before and post application of pesticide. Samples were analysed for 3,5,6-trichloro-2-pyridinol (TCP), the major urinary metabolite of chlorpyrifos, using an enzymatic pre-treatment for extraction and HPLC-MS/MS. Absorbed daily doses (ADD) of chlorpyrifos for farmers were subsequently estimated from the urinary TCP levels. The baseline and postapplication exposure levels were evaluated at the 5th, 50th, and 95th percentile representing low, medium and high-exposure groups in the population. Regression analysis was applied to examine the association between exposure level and factors. The baseline exposure level, which ranged from 0.03 to 1.98 mg/kg/day was below the chronic guidelines recommended by international and national bodies. However, the post-application exposure level, which ranged from 0.35 to 94 mg/kg/day exceeded most of the acute guidelines at the 95th percentile level. Multivariate analysis provided strong evidence for a relationship between post-application exposure level and amount of chlorpyrifos used, as well as body coverage of personal protective equipment.