Rice straw is a major kind of biomass that can be utilized as lignocellulosic materials and renewable energy. Rapid prediction of the lignocellulose (cellulose, hemicellulose, and lignin) and organic elements (carbon, hydrogen, nitrogen, and sulfur) of rice straw would help to decipher its growth mechanisms and thereby improve its sustainable usages. In this study, 364 rice straw samples featuring different rice subspecies (japonica and indica), growing seasons (early-, middle-, and late-season), and growing environments (irrigated and rainfed) were collected, the differences among which were examined by multivariate analysis of variance. Statistic results showed that the cellulose content exhibited significant differences among different growing seasons at a significant level (p< 0.01), and the contents of cellulose and nitrogen had significant differences between different growing environments (p< 0.01). Near infrared reflectance spectroscopy (NIRS) models for predicting the lignocellulosic and organic elements were developed based on two algorithms including partial least squares (PLS) and competitive adaptive reweighted sampling-partial least squares (CARS-PLS). Modeling results showed that most CARS-PLS models are of higher accuracy than the PLS models, possibly because the CARS-PLS models selected optimal combinations of wavenumbers, which might have enhanced the signal of chemical bonds and thereby improved the predictive efficiency. As a major contributor to the applications of rice straw, the nitrogen content was predicted precisely by the CARS-PLS model. Generally, the CARS-PLS models efficiently quantified the lignocellulose and organic elements of a wide variety of rice straw. The acceptable accuracy of the models allowed their practical applications.