The aim of this study is to explore the potential of technology for detecting mind wandering, particularly during video-based distance learning, with the ultimate benefit of improving learning outcomes. To overcome the challenges of previous mind wandering research in ecological validity, sample balance, and dataset size, this study utilized practical electroencephalography (EEG) recording hardware and designed a paradigm consisting of viewing short-duration video lectures under a focused learning condition and a future planning condition. Participants estimated statistics of their attentional state at the end of each video, and we combined this rating scale feedback with self-caught key press responses during video watching to obtain binary labels for classifier training. EEG was recorded using an 8-channel system, and spatial covariance features processed by Riemannian geometry were employed. The results demonstrate that a radial basis function kernel support vector machine classifier, using Riemannian-processed covariance features from delta, theta, alpha, and beta bands, can detect mind wandering with a mean area under the receiver operating characteristic curve (AUC) of 0.876 for within-participant classification and AUC of 0.703 for cross-lecture classification. Furthermore, our results suggest that a short duration of training data is sufficient to train a classifier for online decoding, as cross-lecture classification remained at an average AUC of 0.689 when using 70% of the training set (about 9 min). The findings highlight the potential for practical EEG hardware in detecting mind wandering with high accuracy, which has potential application to improving learning outcomes during video-based distance learning.