A flow injection type hydrogen peroxide detection system with a sub-ppb detection limit has been developed to determine hydrogen peroxide concentration in water sampled from a high temperature, high pressure hydrogen peroxide water loop. The hydrogen peroxide detector is based on luminol chemiluminescence spectroscopy. A small amount of sample water (20 μl) is mixed with a reagent mixture, an aqueous solution of luminol and Co2+ catalyst, in a mixing cell which is installed just upstream from the detection cell. The optimum values for pH and the concentrations of luminol and Co2+ ion have been determined to ensure a lower detectable limit and a higher reproducibility. The photocurrent detected by the detection system is expressed by a linear function of the hydrogen peroxide concentration in the region of lower concentration ([H2O2]≤10ppb), while it is expressed by a quadratic function of [H2O2] in the region of higher concentration ([H2O2]>10ppb). The luminous intensity of luminol chemiluminescence is the highest when pH of the reagent mixture is 11.0. Optimization of the major parameters gives the lowest detectable limit of 0.3 ppb.