Adoption of no-till systems in Eastern Washington has been slow due to the difficulty of managing wheat (Triticum aestivum L.) straw residue and the unknown decomposition potential of cultivars. We hypothesize that by analyzing wheat straw with near-infrared spectroscopy (NIRS), calibration models can be developed to accurately predict fiber and chemical constituents of wheat, determining straw decomposition potential. Straw from a panel of 480 soft winter wheat cultivars adapted to the Pacific Northwest are analyzed for neutral detergent fiber (NDF), acid detergent fiber (ADF), acid detergent lignin (ADL), cellulose, hemicellulose, carbon (C), and nitrogen (N). Using modified partial least squares regression and cross validation techniques, specific environment and broad-based NIRS models are calibrated and predictive ability is validated. R2cal values from broad models are better than the specific models, and are 0.85 (NDF), 0.86 (ADF), 0.65 (ADL), 0.88 (cellulose), 0.42 (hemicellulose), 0.67 (C), and 0.73 (N). The corresponding SEP values are 1.68% (NDF), 1.54% (ADF), 0.62% (ADL), 1.14% (cellulose), 1.11% (hemicellulose), 1.23% (C), and 0.06% (N). A Finch × Eltan breeding population is used to further validate models and prediction accuracies for variety selection within a breeding program scenario. The broad NIRS models prove useful for estimating high and low ranges of NDF, ADF, and cellulose in wheat cultivars which translate into characteristics of slow and fast decomposition potential.