Two hydrogen‐related donors in anatase TiO2—interstitial hydrogen (normalHnormali) and hydrogen substituting for oxygen (normalHnormalO)—are addressed by means of ab initio density functional theory and vibrational mode spectroscopy. First‐principles calculations and infrared (IR) absorption measurements reveal that normalHnormali forms an OH bond lying in the basal plane of the crystal characterized by a stretch local vibrational mode (LVM) with a frequency of 3412 cm−1. According to the calculations, the vibrational spectrum of the threefold‐coordinated hydrogen in normalHnormalO includes two stretch LVMs with the frequencies of 1014 and 1294 cm−1. The theoretically predicted modes occur within the strong two‐phonon absorption band of TiO2, so the conclusions of theory cannot be verified by conventional IR absorption spectroscopy. In accordance with experimental findings, normalHnormali is shown to be unstable at room temperature, whereby formation of interstitial normalH2 should be a preferential sink for hydrogen in defect‐free anatase. It is also found that of normalH2, normalHnormali, and normalHnormalO, the latter is the most energetically favorable defect, which may account for the “hidden” hydrogen unavailable for the standard spectroscopic techniques.