Discrepancies of one pH unit and more have been observed after a few days, between continuous on-line in situ pH measurements and instant off-line pH measurements during anaerobic digestion of an agroindustrial wastewater. Concomitantly, the electrical resistance across the porous diaphragm of the on-line electrode increased, and a black clogging developed on its diaphragm. Measurements of the relative liquid junction potential in KCl or Na(2)S solutions excluded that high concentrations of ions such as, K(+), Na(+), Cl(-), HS(-), or S(2-) were the major cause of the drifts in pH values. It has been possible to limit the rapid increase of the liquid junction potential and the black clogging formation on the porous diaphragm either by acidification and/or by overpressurization of the electrode-filling liquid. Continuous on-line in situ pH values consistent with instant off-line pH values over long periods of time have been obtained with a newly designed pH sensor in which a special jellied electrode filling replaced the porous diaphragm.