Abstract: A kind of combination analysis method which consists of pH value test, chemiluminescence test of luminol, ash test, X- Ray Fluorescence ( XRF) analysis and X- Ray Diffraction ( XRD) analysis was developed to detect four kinds of illegal additives, such as calcium peroxide, big white powder ( calcium carbonate) , gypsum powder ( calcium sulfate) and talc powder in wheat flour.The species of analytes were judged basically by pH value test, and oxidation characteristics by luminol chemiluminescence reaction test.Before XRF test which provided the main elements in the analytes and XRD test which provided the structure infromation, the samples were enriched through ash test.According to the analysis method and instrument sensitivity, the semi- quantitation limit value of calcium peroxide, calcium carbonate, calcium sulfate and talc in wheat flour was determined as 0.05%, 0.5%, 0.5%, 2% respectively.The method had the advantages of easy operation, rapid and accurate, can be based on actual need to combination analysis.