Parasitic reactions, such as evolution of hydrogen at the negative electrode, can occur under the operating conditions of flow batteries and other electrochemical systems. Such parasitic reactions can undesirably impact operating performance by altering the pH and/or state of charge of one or both electrolyte solutions in a flow battery. Electrochemical balancing cells can allow adjustment of electrolyte solutions to take place. Electrochemical balancing cells suitable for placement in fluid communication with both electrolyte solutions of a flow battery can include: a first chamber containing a first electrode, a second chamber containing a second electrode, a third chamber disposed between the first chamber and the second chamber, a cation-selective membrane forming a first interface between the first chamber and the third chamber, and a bipolar membrane, a cation-selective membrane, or a membrane electrode assembly forming a second interface between the second chamber and the third chamber.