Personnel in Isolated, Confined, and Extreme (ICE) environments face unique psychological stressors that can compromise performance, safety, and mission success. Traditional psychological monitoring approaches, predominantly retrospective questionnaires and clinical interviews, may inadequately capture the dynamic nature of psychological adaptation in these demanding contexts. This mini-review examines the potential role of Ecological Momentary Assessment (EMA) as part of a comprehensive approach to psychological monitoring in ICE environments. We review current monitoring practices across spaceflight, polar, submarine, and remote field operations, and evaluate emerging technologies including EMA, wearable sensors, and digital biomarkers. While EMA offers theoretical advantages through real-time data collection and reduced recall bias, implementation faces substantial obstacles including technological constraints, participant burden, cultural considerations, and validation challenges. Limited empirical evidence suggests that hybrid approaches combining multiple assessment modalities may be most promising for operational implementation. We propose a framework for developing next-generation psychological monitoring systems that balance scientific rigor with operational feasibility, emphasizing environment-specific validation and the inherent sample-size constraints of ICE settings.