Bioimpedance is a simple and non-invasive method of assessing body fluid composition. The aim of our study was to evaluate the reilability of impedance: a) to measure urea distribution volume considered to be coextensive with total body water (TBW); b) to assess the changes in body fluid compartments before and after dialysis; c) to predict hypotensive episodes. In twelve hemodialysis patients, TBW measured by bioelectrical impedance analysis (BIA) before a dialysis session was significantly correlated with the urea distribution volume estimated by dialysis direct quantification (r = 0.64, p < 0.05) and with TBW calculated by the Watson equation (r = 0.65, p < 0.05). Anthropometric values were, on average, 4.8% higher. TBW measured by BIA at the end of treatment overestimated fluid losses induced by ultrafiltration by 14% to 70%, while TBW 6 h after dialysis reflected the weight losses. On line BIA during hemodialysis has a very low positive predictive value (41.6%) and poor sensitivity (66%) for the prediction of hypotension. In conclusion, BIA is helpful in assessing the urea distribution volume but is not reliable for assessing acute fluid changes nor for predicting hypotensive episodes related to hemodialysis.