The phase transformations of the Ti38V30Cr14Mn18 alloy during hydrogenation and dehydrogenation using deuterium (D2) were investigated using in situ neutron powder diffraction (NPD) at various D2 pressures up to 2 MPa. Initially, the first hydride that formed, Ti38V30Cr14Mn18D15, had the same body centered cubic (BCC) crystal structure as the starting alloy. Upon further hydrogenation, the system displays a distinct two-phase mixture of the intermediate BCC and body-centered tetragonal (BCT) phases, that exist in a ration of 1.38:1.42, respectively. At the end of the deuterium absorption, the phase pure Ti38V30Cr14Mn18D183 material forms, with a face-centered cubic (FCC) structure. Upon dehydrogenation, all hydride phases eventually returned to the initial alloy phase without any amorphization or disproportionation. Using standard Rietveld refinement, information on the variation of the deuterium site occupancy, the lattice symmetry, and the cell volume were determined during these phase changes and are presented.