To evaluate the applicability of non-invasive visible and near infrared (VIS-NIR) spectroscopy for determining ethanol concentration of Chinese rice wine in square brown glass bottle, transmission spectra of 100 bottled Chinese rice wine samples were collected in the spectral range of 350-1200 nm. Statistical equations were established between the reference data and VIS-NIR spectra by partial least squares (PLS) regression method. Performance of three kinds of mathematical treatment of spectra (original spectra, first derivative spectra and second derivative spectra) were also discussed. The PLS models of original spectra turned out better results, with higher correlation coefficient in calibration (Rcal) of 0.89, lower root mean standard error of calibration (RMSEC) of 0.165, and lower root mean standard error of cross validation (RMSECV) of 0.179. Using original spectra, PLS models for ethanol concentration prediction were developed. The Rcal and the correlation coefficient in validation (Rval) were 0.928 and 0.875, respectively; and the RMSEC and the root mean standard error of validation (RMSEP) were 0.135 (%, v v-1) and 0.177 (%, v v-1), respectively. The results demonstrated that VIS-NIR spectroscopy could be used to predict ethanol concentration in bottled Chinese rice wine.