Human endurance in underwater locomotion is fundamentally restricted by high energetic demands to overcome drag and the finite supply of self-contained breathing gas. While exoskeleton technology can reduce the metabolic cost of humans in terrestrial locomotion, its potential to enhance human endurance during underwater diving remains entirely unexplored. Here, we present DiveMate, a field-deployable, untethered exoskeleton designed to improve human diving endurance via adaptive kick assistance in real-world underwater environments. During naturalistic diving, DiveMate increases the travel distance using a given energy (breathing gas) by 42.9% and extends dive duration by 54.9% through reducing gas consumption rate. Marked reductions in muscle activation indicate a decrease in physiological exertion, with the net gas consumption rate decreasing by 47.0%. Kinematic characteristics and regularity improvements further underpin efficient energy economy. These results suggest that applying exoskeleton assistance is beneficial for improving human diving endurance and augmenting their ability to explore the aquatic world. This study extends the application frontier of exoskeletons and provides a potential reference for the design and assessment of future underwater assistive devices.