Abstract: Authenticity identification of Daohuaxiang rice was studied by combing of proton nuclear magnetic resonance(~1H NMR) and multivariate analysis in this paper.~1H NMR spectra were acquired for Daohuaxiang and adulteration samples. The compositional patterns of Daohuaxiang and adulteration samples were analyzed using their ~1H NMR spectra.Then two Daohuaxiang identification models were built based on ~1H NMR spectroscopy and semi- quantitative information of 20 compounds of the rice samples respectively. It turned out that there were 16 significantly different( p < 0.05) compounds between Daohuaxiang and adulteration rice including alpha- glucose,starch,sucrose,betaine,beta- glucose,choline,asparagine,aspartate,succinate,glutamate,acetate,gamma aminobutyric acid( GABA),alanine,threonine,isoleucine,and valine. The predictive accuracies were 83.5% and70.1% for ~1H NMR spectroscopy- based identification model and semi- quantitative information- based identification model respectively.