A novel method for the detection of hydrogen peroxide in aqueous solution was developed via reaction between H2O2, trivalent titanium ion (Ti3+) and 4-(2-thiazolylazo) resorcinol (TAR), resulting in a ternary complex with a maximum UV absorbance at 530 nm. The CE detection of H2O2 was fast, sensitive and cost-effective without pretreatment procedures. H2O2 was detected within 15 min at 1 to 100 μM range with the lowest detection limit at 1.0 μM. Under the optimized CE conditions, the concentration of H2O2 in coffee or tea extract was quantitatively determined. Our results show that CE detection of the ternary complex of H2O2-Ti3+-TAR has potential applications for the detection of H2O2 in aqueous sources.