Indolizine derivatives are of great interest as fluorescent emitters for peroxyoxalate chemiluminescence. The reaction of peroxyoxalates such as bis-(2,4,6-trichlorophenyl) oxalate (TCPO) with H2O2 can transfer energy to fluorescer via the formation of dioxetanedione intermediate. Four indolizine derivatives were used as a novel fluorescer in the chemiluminescence (CL) systems in this study. The relationship between CL intensity and the concentration of fluorescer, peroxyoxalate, sodium salicylate and hydrogen peroxide was investigated. Optimum conditions were obtained for four fluorescers and it was found that the indolizine can be used as an efficient green fluorescence emitter. Vitamin B6 induces a sharp decrease in the CL intensity of the TCPO–hydrogen peroxide–sodiumsalicylate system. A simple, rapid and sensitive CL method for the determination of vitamin B6 has been developed. The results showed a linear relationship between vitamin B6 concentration and peroxyoxalate CL intensity in the range 7.0× 108–1.0× 104. A detection limit of 2.3× 108 M and relative standard deviation (RSD) of <4.5% were obtained.