An integrated study has been carried out to elucidate the distribution and occurrence of arsenic in selected groundwater samples in the area of Sherajdikhan, Bangladesh. Arsenic and other parameters (T, pH, EC, Na+, K+, Ca2+, Mg2+, Cl−, NO3−, SO42−, HCO3−, PO43−, Fe, Mn and DOC) have been measured in groundwater samples collected from shallow/deep tube wells at different depths. Hydrogeochemical data suggest that the groundwaters are generally Ca–Mg–HCO3 and Mg–Ca–HCO3 types with bicarbonate (HCO3−) as the dominant anion, though the other type of water has also been observed. Dissolved arsenic in groundwater ranged from 0.006 to 0.461 mg/l, with 69% groundwater samples exceeded the Bangladesh limit for safe drinking water (0.05 mg/l). Correlation and principal component analysis have been performed to find out possible relationships among the examined parameters in groundwater. Low concentrations of NO3− and SO42−, and high concentrations of DOC, HCO3− and PO43− indicate the reducing condition of subsurface aquifer where sediments are deposited with abundant organic matter. Distinct relationship of As with Fe and Mn, and strong correlation with DOC suggests that the biodegradation of organic matter along with reductive dissolution of Fe–Mn oxyhydroxides has being considered the dominant process to release As in the aquifers studied herein.