We have detected the occurrence of hydrogen bonding involving an interstitial positive muon situated between hydrogen atoms of two independent alanate anions in sodium alanate (NaAlH4). Ti doping, which is known to dramatically improve the hydrogen cycling performance of NaAlH4, reduces the kinetic barrier of the transition of the muon from the muon-dialanate state to a mobile interstitial state. This observation strongly suggests that hydrogen bonding is the primary bottleneck for hydrogen release or uptake in sodium alanate, which might be common to other complex hydrides.