The deep red luminescence of in the distorted perovskite is reported and discussed. The excitation spectrum of luminescence is dominated by the to charge‐transfer transition at . The luminescence is due to the transition with the zero‐phonon line at and the associated side bands at longer wavelengths. Evidence is presented for the occurrence of multiple sites in the host lattice. This is attributed to the deviation from a perfect 1:1 order between the B‐site ions of the perovskite lattice. The unactivated host lattice also exhibits luminescence due to the presence of this ion as an impurity in one of the starting materials . Evidence is presented for to energy transfer in this host lattice.