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Water accumulation in goafs in Chinese coal mines is a major hidden hazard that can trigger water inrush accidents and may also affect aquifer integrity and regional water security. Reliable delineation of goaf water distribution and identification of water-source types are therefore essential for mine water-hazard control and groundwater protection. This paper reviews the main technical routes for goaf groundwater investigation, including geophysical prospecting, hydrogeochemical and isotopic identification, direct inspection tools, and data-driven intelligent workflows. For geophysical detection, the mechanisms, engineering applicability, and key constraints of the Transient Electromagnetic Method (TEM), Surface Nuclear Magnetic Resonance (NMR), the High-Density Resistivity Method (HDRM), and the Coherent Frequency Component (CFC) electromagnetic wave reflection coherence method are synthesized, with emphasis on interpretation boundaries and uncertainty sources under complex geological conditions. For source identification, conventional hydrochemistry, stable isotopes, and laser-induced fluorescence are summarized, and intelligent recognition models such as neural networks and support vector machines are discussed in terms of workflow positioning and practical performance limits. A unified evaluation rationale is established and a semi-quantitative method–metric matrix is constructed to compare techniques in terms of reliability, deployability, cost level, environmental adaptability, and information value, thereby clarifying their functional roles and complementarities within staged engineering workflows. The synthesis indicates that major bottlenecks include limited deep capability under strong interference, pronounced interpretational non-uniqueness caused by complex geology and irregular goaf geometries, and constrained timeliness and generalization for mixed-source identification. Future directions are summarized as multi-method integration with fusion-driven interpretation, intelligent and quantitative decision support with quality control, and sensor–platform advances enabling more practical three-dimensional investigation, aiming to improve the reliability and engineering usability of goaf groundwater hazard assessment.