A new type of halogen-free flame retardant has been synthesized with raw materials of Di(trimethylolpropane) and phosphorus oxychloride, and the influence of the raw material ratio, reaction temperature and reaction time on the yield has been discussed. Furthermore, the flame-retardant combustion performance has been tested by vertical burning test. The flame-retardant effect and thermal stability of the target product on different fabrics have been investigated, and the structures of the intermediates and the target products were characterized by Fourier transform infrared spectrometer. After discussing the different flame-retardant effects on different fabrics, the conclusions have been drawn: The Di(trimethylolpropane) biphosphate ethanolamine salt has different flame-retardant effects on polyester, acrylic, chinlon, cotton and blended fabrics, of which the flame-retardant effect on chinlon, polyester and cotton is fairly good, but the flame-retardant effect is unremarkable for blended fabrics and acrylic.