The principal objective of current study was to evaluate the potential of near infrared reflectance spectroscopy (NIRS) as a non-destructive method for the prediction of the amylose and protein contents of un-hulled and brown rice in broad-based calibration models. The average amylose and protein content of 75 rice accessions were 20.3% and 7.1%, respectively. Additionally, the range of amylose and protein content were 16.6-24.5% and 3.8-9.3%, respectively. In total, 79 rice germplasms representing a wide range of chemical characteristics, variable physical properties, and origins were scanned via NIRS for calibration and validation equations. The un-hulled and brown rice samples evidenced distinctly different patterns in a wavelength range from 1,440 nm to 2,400 nm in the original NIR spectra. The optimal performance calibration model could be obtained by MPLS (modified partial least squares) using the first derivative method (1:4:4:1) for un-hulled rice and the second derivative method (2:4:4:1) for brown rice. The correlation coefficients $(r^2)$ and standard error of calibration (SEC) of protein and amylose contents for the un-hulled rice were 0.86, 2.48, and 0.84, 1.13, respectively. The $r^2$ and SEC of protein and amylose content for brown rice were 0.95, 1.09 and 0.94, 0.42, respectively. The results of this study suggest that the NIRS technique could be utilized as a routine procedure for the quantification of protein and amylose contents in large accessions of un-hulled rice germplasms.