A monoclinic phase isostructural to Al4W was revealed in Al–Ni–Re close to the Al–Re terminal. It is assumed to be a ternary extension of the high-temperature Al4Re phase usually transforming in binary alloys even by sharp quenching from the existence temperatures. The powder X-ray diffraction pattern of this phase of the Al77Ni2.5Re20.5 composition was indexed for the Cm space group with a=5.1538(12) Å, b=17.410(5) Å, c=5.1546(15) Å, and β=100.548(16)°.