Titanium catecholate complexes can be desirable active materials for flow batteries and other electrochemical energy storage systems, particularly when incorporated in aqueous electrolyte solutions. It can be desirable to avoid introducing certain organic solvents and/or extraneous salts into aqueous electrolyte solutions. Methods for synthesizing titanium catecholate complexes that can help avoid the unwanted introduction of organic solvents and/or extraneous salts into aqueous electrolyte solutions can include: providing an aqueous solution containing a catechol compound, reacting a titanium reagent with the catechol compound in the aqueous solution to form an intermediate titanium catecholate complex, isolating the intermediate titanium catecholate complex as a solid or slurry, and reacting a ligatable compound with the intermediate titanium catecholate complex in the presence of a base to produce a salt form titanium catecholate complex containing at least one additional ligand.