Previous studies have primarily focused on the extraction of highland barley crops using single phenological images, which ignored the selection of the optimal phenological period for classification. Utilizing the multiple phenological images from Sentinel-2 to construct 25 features, including spectral, red edge, vegetation, and texture features, the recursive feature elimination algorithm and the random forest algorithm (RF) were employed to optimize feature datasets for different phenological stages, which were then used for the identification and classification of high-land barley by RF. The main results were as follows: (1) Information extraction based on feature optimization combinations yielded good overall classification accuracy, with classification accuracies for highland barley being 92.56% (jointing stage), 90.90% (heading stage), 90.74% (flowering stage), 91.55% (milk ripening stage), and 90.51% (maturity stage), respectively. (2) NDVIre1 had the highest importance score (0.1792) in the feature selection combination, indicating that the red edge index contributed significantly to crop information extraction and classification. (3) The five feature variables—GLCM_Mean, RVI, homogeneity, MAX, and GLCM_Correlation—showed stability and universality in the extraction of highland barley. These results demonstrated that the images that derived from the jointing and milk ripening phenological stages had the best applicability for highland barley extraction, and the optimized feature datasets that composed of NDVIre1 were conductive to detect and monitor of highland barley crops in the mountainous regions of northwest China.