The integration of neurophysiological techniques into Industry 5.0 represents a transformative approach to assessing human factors in real-world operational settings. This study presents a systematic review of existing literature to evaluate the application of neurophysiological methods in assessing cognitive and emotional states, such as workload, stress, attention, and trust, within industrial environments. A total of X peer-reviewed articles published between 2018 and 2024 were analyzed following a structured methodology. The findings reveal that EEG (45%), eye-tracking (30%), EDA (20%), and ECG (15%) are the most frequently adopted techniques for monitoring cognitive and emotional responses. Additionally, 60% of the studies focused on stress and workload assessment, while only 25% examined trust and collaboration in human–robot interaction, highlighting a gap in comprehensive teamwork analysis. Furthermore, only 35% of the studies validated their approaches in real-world industrial settings, emphasizing a significant limitation in ecological validity. The review also identifies that multimodal integration remains underexplored, with just 15% of studies combining multiple neurophysiological signals for a more holistic assessment. These results indicate a growing but still fragmented research landscape, with clear opportunities for expanding real-world applications, improving methodological standardization, and fostering interdisciplinary collaboration. Future research should prioritize validation in dynamic, real-life work environments and explore the synergistic potential of multimodal neurophysiological approaches to enhance human-centred industrial systems.