X-ray studies of iron chalcogenide FeTe0.65Se0.35 single crystals were performed after they were exposed in air and hydrogen atmospheres at room and high temperatures, for long periods of time. It is found that impurity components have a significant effect on the structural characteristics of the diffraction pattern for this layered tetragonal superconducting material. It is shown that molecular impurities do not change the matrix symmetry of the tetragonal substitution solutions. However, when hydrogen molecules dissociate close to 200 °C under the thermocatalytic effect of Fe atoms, the tetragonal lattice of the matrix becomes unstable. Symmetry is reduced against the background of an increased concentration of atomic hydrogen and strengthening of the chemical bonds in the crystals. The crystal density sharply increases, and a FeTe0.65Se0.35 + H interstitial solution based on an orthorhombic lattice is formed. It is shown that the structural tetra-ortho phase transition in such solutions occurs near 200 °C.