Abstractβ‐TlReO4, the room temperature modification of thallium perrhenate, has been investigated by means of single crystal X‐ray diffraction. It crystallizes in the monoclinic space group P1121/a with a = 5.636(1), b = 17.428(3), c = 13.353(3) Å, γ = 89.86(2)° and Z = 12. The structure has been refined to R = 0.063 (wR = 0.053) using 2 020 absorption‐corrected reflections. The title compound can be described as an intergrowth of β‐CsReO4and scheelite type blocks at unit cell level. The structure of β‐TlReO4consists of isolated ReO4tetrahedra linked together by TlO8and TlO9polyhedra. Based upon group theoretical considerations the structural relationships between β‐TlReO4, β‐CsReO4, α‐CsReO4and sche