In oats (Avena sativa L.), groat percentage (GP) is defined as the amount of hull-less kernels obtained after de-hulling, expressed as a percentage of the weight of the sample. GP is considered a good marker of milling yield in oats, but so far a quick and reliable method to define it has been lacking. In the present study, a group of oat cultivars, grown in Italy in 1998–2000, was used to develop near infrared (NIR) spectroscopy calibration equations for this parameter. The material for the analysis was represented by whole kernels. The coefficient of determination R2c was 0.80. The ability of the equation to predict GP was then verified using a separate set of oat samples. These preliminary results indicated that NIR spectroscopy could be considered a good tool to predict GP in oat cultivars; analysis of whole kernels allowed time to be saved by avoiding the grinding stage in sample preparation.