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Brain–computer interfaces (BCIs) require efficient feature extraction and dimensionality reduction from high-dimensional neural signals. Electroencephalogram (EEG) microstate analysis is a rapid and noise-resistant approach that classifies instantaneous EEG states into several spatial distribution patterns (templates). Previous BCI studies using the EEG microstate approach have typically used aggregated metrics, such as duration, frequency of occurrence, or time coverage, and have rarely applied pointwise microstate labeling as temporally ordered, one-dimensional sequences for robust classification. Moreover, the physiological relevance of EEG topographic polarity has often been overlooked, despite its potential to reveal smoother state transitions and align with event-related potential components. In this study, we applied polarity-considered microstate labeling to stimulus-driven classification in an oddball paradigm. EEG data from 40 healthy participants (20 per response type) were analyzed across three factors: stimulus modality (auditory or visual), modality condition (unimodal or cross-modal), and response type (key-response task or mental counting task). Preprocessed 32-channel EEG data were labeled with microstate templates (A–E ± topographical polarity) using a winner-take-all approach, and the resulting sequences were classified using multiple machine-learning models. The results showed that tree-based ensemble models (Random Forest, XGBoost, and CatBoost) achieved the most stable and accurate performance in the key-response task with cross-modal visual targets. These models reached an area under the receiver operating characteristic curve above 0.8 and a mean F1 score of 0.83. Preserving polarity improved classification by approximately 20% across tasks, doubling the label-space granularity and revealing temporal patterns aligned with the N200 and P300 components. Visual stimuli generally outperformed auditory stimuli, and cross-modal benefits emerged primarily in key-response tasks. These findings demonstrate that polarity-considered microstate labeling enhances classification accuracy and interpretability in BCIs. This method highlights the potential for real-time applications, such as P300 spellers and multimodal attention monitoring.