Laser-ablated Hf atoms react with H2O2 and with H-2 + O-2 mixtures in solid argon to form the Hf(OH)2 and Hf(OH)4 molecules, which are identified from the effect of isotopic substitution on the matrix infrared spectra. Electronic structure calculations at the MP2 level varying all bond lengths and angles converge to nearly linear and tetrahedral molecules, respectively, and predict frequencies for these new product molecules and mixed isotopic substituted molecules of lower symmetry that are in excellent agreement with observed values, which confirms the identification of these hafnium hydroxide molecules. This work provides the first evidence for a metal tetrahydroxide molecule and shows that the metal atom reaction with H2O2 in excess argon can be used to form pure metal tetrahydroxide molecules, which are not stable in the solid state.