The chromaticity coordinates and luminance factor are important indicators of the fluorescent dyeing performance of fluorescent dyed fabric. However, with the current bleaching pretreatment process, the chromaticity coordinates and luminance factor of fluorescent yellow dyed modacrylic/cotton blended fabric usually do not meet the requirements of standard ISO 20471. Here we report a new type of bleaching process method via sodium chlorite to solve the problem of yellowing of the background color of the modacrylic/cotton blended fabric. Compared with hydrogen peroxide bleaching, the whiteness of the modacrylic/cotton blended fabric was increased by 13.52% with sodium chlorite bleaching. The color performance analysis showed that the chromaticity coordinates and luminance factor of fluorescent yellow dyed modacrylic/cotton fabric after exposure to xenon light or washing cycles could meet the standard ISO 20471 requirements. Moreover, the fluorescent yellow dyed fabric has good color fastness, such as rubbing resistance, perspiration, laundering at 60°C, and dimensional stability. In addition, the fluorescent yellow dyed blended fabric also has flame retardant performance. Our work may provide a method for the preparation of high-visibility fluorescent yellow fabric with flame retardant performance. It could be used for multifunctional personal protective equipment.