Mental stress is an increasingly common psychological issue leading to diseases such as depression, addiction, and heart attack. In this study, an early detection framework based on electroencephalogram (EEG) data is developed for reducing the risk of these diseases. In existing frameworks, signals are often segmented into smaller sections prior to being input to a deep neural network. However, this approach ignores the fundamental nature of EEG signals as a carrier of valuable information (e.g., the integrity of frequency and phase, and temporal fluctuations of EEG components). As such, this type of segmenting may lead to information loss and a failure to effectively identify mental stress levels. Thus, we propose a novel multiclass classification framework termed multibranch LSTM and hierarchical temporal attention (MuLHiTA) for the early identification of mental stress levels. It specifically focuses on not only intraslice (within each slice) but also interslice (between different slices) samples in parallel. This was achieved by including two complementary branches, each of which integrated a specifically designed attention module into a bidirectional long short-term memory (BLSTM) network, enabling extraction of the most discriminative features from interslice and intraslice EEG signals simultaneously. The outputs of attention modules were then summed to obtain a feature representation that contributes to reduce overfitting and more effective multiclass classification. In addition, electrode positions were optimized using neural activity areas under high-stress conditions, thereby reducing computational costs by minimizing the number of critical electrodes. MuLHiTA was evaluated across one private [Montreal imaging stress task (MIST)] and two publicly available EEG datasets [EEG during mental arithmetic tasks (DMAT) and Simultaneous task EEG workload (STEW)]. These were divided into training and test sets using an 8:2 ratio, and the training data were further divided into training and validation sets using a fivefold cross-validation (CV) method, in which the model with the highest accuracy among the five was selected. The model was trained once more with the full training set, and the test data were then used to evaluate its performance. This approach achieved average classification accuracies of 93.58%, 91.80%, and 99.71% for the MIST, STEW, and DMAT datasets, respectively. Experimental results showed MuLHiTA was superior to state-of-the-art algorithms, including EEGNet, BLSTM, EEGLearn, convolutional neural network (CNN)-long short-term memory (LSTM), and convolutional recurrent attention model (CRAM), for multiclass classification. This demonstrates the viability of MuLHiTA for the early detection of mental stress.