Compounding climate extremes threaten ecosystems, agriculture, and public health, with intensification driven by a warming climate and increasing human interventions. However, the global linkage between temperature extremes and total water storage (TWS) deficits remains insufficiently explored. Here, we analyzed 22 years (2002–2024) of Gravity Recovery and Climate Experiment (GRACE) and GRACE-FO satellite data to examine the spatiotemporal coincidence of elevated temperatures and TWS deficits and explore their bidirectional predictability. We find that low TWS episodes frequently coincide with or lag temperature extremes by about one month in major land–atmosphere coupling hotspots, including equatorial, subtropical, and mid-latitude regions, possibly due to enhanced evapotranspiration and soil moisture reductions. Pre-existing TWS deficits appear to intensify and prolong temperature extremes by reducing latent heat flux and increasing sensible heat flux, potentially creating feedback processes that amplify drought and thermal stress; however, these mechanisms warrant further investigation. Statistical tests confirm that these co-occurrences are unlikely to be random, whereas Granger predictability analysis demonstrates that temperature anomalies improve forecasts of subsequent TWS extremes in critical regions. Overall, our results underscore the vulnerability of water-limited areas under climate change and highlight the value of continuous TWS monitoring to better predict and mitigate the impacts of temperature extremes. They further emphasize the urgency of integrated water-resource management and adaptation strategies in regions prone to prolonged compound extremes.