Near-infrared spectroscopy (NIRS) holds significant promise in detecting food adulteration due to its non-destructive, simple, and user-friendly properties. This study employed NIRS in conjunction with chemometrics to estimate the content of low-price rice flours (Nanjing, Songjing, Jiangxi silk, Yunhui) blended with high-price rice (Wuchang and Thai fragrant). Partial least squares regression (PLSR), support vector regression (SVR), and back-propagation neural network (BPNN) models were deployed to analyze the spectral data of adulterated samples and assess the degree of contamination. Various preprocessing techniques, parameter optimization strategies, and wavelength selection methods were employed to enhance model accuracy. With correlation coefficients exceeding 87%, the BPNN models exhibited high accuracy in estimating adulteration levels in high-price rice. The SPXY-SG-BPNN, SPXY-MMN-BPNN, KS-SNV-BPNN, and SPXY-SG-BPNN models showcased exceptional performance in discerning mixed Wuchang japonica, Thai fragrant indica, and Thai fragrant Yunhui rice. As shown above, NIRS demonstrated its potential as a rapid, non-destructive method for detecting low-price rice in premium rice blends. Future studies should be performed to concentrate on enhancing the models’ versatility and practical applicability.