Arsenic contamination in water has caused severe health problems around the world. The purpose of this study was to evaluate the geological and anthropogenic aspects of As pollution in surface and groundwater resources of Jamshoro Sindh, Pakistan. Hydride generator atomic absorption spectrophotometry (HG-AAS) is employed for the determination of arsenic in water samples, with detection limit of 0.02 microg l(-1). Arsenic concentrations in surface and underground water range from 3.0 to 50.0, and 13 to 106 microg l(-1), respectively. In most of the water samples As levels exceeded the WHO provisional guideline values 10 microg l(-1). The high level of As in under study area may be due to widespread water logging from Indus river irrigation system which causes high saturation of salts in this semi-arid region and lead to enrichment of As in shallow groundwater. Among the physico-chemical parameters, electrical conductivity, Na(+), K(+), and SO(4)(2-) were found to be higher in surface and ground water, while elevated levels of Ca(2+) and Cl(-) were detected only in ground water than WHO permissible limit. The high level of iron was observed in ground water, which is a possible source of As enrichment in the study area. The multivariate technique (cluster analysis) was used for the elucidation of high, medium and low As contaminated areas. It may be concluded that As originate from coal combustion at brick factories and power generation plants, and it was mobilized promotionally by the alkaline nature of the understudy groundwater samples.