Abstract: Analysis of biomass-coal blends is crucial for developing appropriate subsidy policies for biomass co-firing power generation. Visible and near infrared reflectance spectroscopy (Vis/NIRS) was used for qualitative analysis of straw, coal and straw-coal blends, and quantitative analysis of straw content of straw-coal blends. A total of 80 straw samples (particle size less than 80 mm), 9 coal samples (particle size less than 10 mm), 120 straw-coal blends samples with straw content varying from 70% to 99% (blends1) and 120 straw-coal blends samples with straw content varying from 1% to 30% (blends2) were prepared. Vis/NIRS spectra of samples were recorded using a FOSS NIRS DS 2 500 spectrometer. Partial least squares-discriminant analysis (PLS-DA) was used for qualitative analysis while modified partial least squares (MPLS) was used for quantitative analysis. The correct classification percentages (CCP) of straw versus blends1 and coal versus blends 2 were 90.00% (using region 1 100-2 500 nm) and 71.88% (using region 400-2 500 nm), respectively. The ratio of standard error of performance to standard deviation (RPD) for quantitative analysis of straw content of blends1 and blends2 were 2.32 (400-2 500 nm) and 1.48 (400-1 100 nm), respectively. It was concluded that the spectral region from 1100 to 2500 nm is more suitable for classification of straw versus blends1, and the region is also applied in quantitative analysis of straw content of blends1. Likewise, the suitable spectral region for classification of coal versus blends2 is from 400 to 1 100 nm, which is also appropriate for quantitative analysis of straw content of blends2. Vis/NIRS along with chemometrics may be a feasibility way for qualitative and quantitative analysis of straw-coal blends with large particle size.