For buckwheat, the optimal harvest period is difficult to determine-too early or too late a harvest affects the nutritional quality of buckwheat. In this paper, physical and chemical tests are combined with a method using near-infrared spectroscopy nondestructive testing technology to study buckwheat harvest and determine the optimal harvest period. Physical and chemical tests to determine the growth cycle were performed at 83 days, 90 days, 93 days, 96 days, 99 days, and 102 days, in which the buckwheat grain starch, fat, protein, total flavonoid, and total phenol contents were assessed. Spectral images of buckwheat in six different harvest periods were collected using a near-infrared spectral imaging system. Four preprocessing methods (SNV, S-G, DWT, and the normaliz function) and three dimensionality reduction algorithms (IVSO, VCPA, VISSA) were used to process the raw buckwheat spectral data, and the full and eigen spectra were established as a random forest (RF). Random forest (RF) and Least Squares Support Vector Machine (LS-SVM) classification models were used to determine the full and eigen spectra, respectively, and the optimal model for the buckwheat single harvest period was determined and validated. Through physical and chemical tests, it was concluded that the 90-day harvest buckwheat grain protein, fat, and starch contents were the highest, and that the total flavonoid and total phenolic contents were also high. The SNV preprocessing method was the most effective, and the feature bands extracted using the IVSO algorithm were more representative. The IVSO-RF model was the best discriminative model for the classification of buckwheat in different harvest periods, with the correct rates of the training and prediction sets reaching 100% and 96.67%, respectively. When applying the IVSO-RF model to the buckwheat single harvest period to verify the classification, the correct rate of the training set for each harvest period reached 96%, and that of the prediction set reached 100%. Near-infrared spectroscopy combined with the IVSO-RF modeling method for buckwheat harvest period detection is a rapid, nondestructive classification method. When this was combined with physical and chemical analyses, it was determined that a growth cycle of 90 days is the best harvest period for buckwheat. The results of this study can not only improve the quality of buckwheat crops but also be applied to other crops to determine their optimal harvest period.