We investigated the water H-bond network and its dynamics in Ni₂Cl₂BTDD, a prototypical MOF for atmospheric water harvesting, using linear and ultrafast IR spectroscopy. Utilizing isotopic labeling and infrared spectroscopy, we found that water forms an extensive H-bonding network in Ni₂Cl₂BTDD. Further investigation with ultrafast spectroscopy revealed that water can reorient in a confined cone up to ∼50° within 1.3 ps. This large angle reorientation indicates H-bond rearrangement, similar to bulk water. Thus, although the water H-bond network is confined in Ni₂Cl₂BTDD, different from other confined systems, H-bond rearrangement is not hindered. The picosecond H-bond rearrangement in Ni₂Cl₂BTDD corroborates its reversibility with minimal hysteresis in water sorption.