Catalytic reaction of luminol-phenanthroline-H2O2 chemiluminescence by Pb(Ⅱ) was tested by combining flowing-injection and chemiluminescence. Through the single factor experiment about the concentration of luminous, hydrogen peroxide, 1, 10-phenanthroline, the pH value of Pb solution and buffer solutions, the initial was selected and the best condition was designated through orthogonal test. The results showed that Pb (Ⅱ) enhanced the chemiluminescence intensity of luminol-1,10-phenanthroline-H2O2, and the stimulation of Pb(Ⅱ) had a positive correlation with its concentration in drinking water when its concentration ranged from 1.0×107 g/mL to 1.0 ×105 g/mL. It proved to be a rapid method to determine the sudden change of Pb (Ⅱ) in drinking water and to carry out the goalas an early alarming of emergency contamination of Pb (Ⅱ).