The FeO/TFe of iron ore is an important index to evaluate the industrial value of iron ore and classify the industrial type of ore. The conventional FeO/TFe measurements cost a lot of labor with low efficiency and long period, which are not benefit for the economical, reasonable and effective iron ore exploitation. Firstly, the visible and near-infrared spectrums of the BIF samples from Anqian mining area of Liaoning province were measured and the spectral features were analyzed. Then, three indexes of ration index (RI), difference index (DI) and normalized difference index (NDI) were put forward for analyzing the correlation relations between the indexes and FeO/TFe, and exploring the sensitive waveband. The experimental results showed that the sensitive waveband results of FeO/TFe from these three indexes are all located at 935 and 1 050 nm. All of these three correlation coefficients are larger than 0.9 at these two wavelength and the maximum value is 0.971 for the RI. Therefore, the inversion model for FeO/TFe according to RI results can be established and verified based on the laboratory report. The prediction error of FeO/TFe is 0.038 and the coefficient of determination (R2) is 0.964 5. The experimental results can provide a new economical and effective approach for determining the FeO/TFe of BIF and mine exploring via remote sensing.