Here, we present the synthesis and crystal structure of Rb3InCl6 prepared from air stable reagents via a two-step process that proceeds through the intermediate Rb2InCl5 center dot H2O. Rb3InCl6 crystallizes with the Rb3YCl6 structure type (C2/c), which can be derived from the double perovskite structure by noncooperative tilting of isolated [InCl6](3)(-) octahedra. Despite this lowering of symmetry, the optical properties are similar to the cubic double perovskite Cs2NaInCl6. Partial substitution of In3+ with Sb3+ in Rb3InCl6 results in intense cyan-green photoluminescence originating from localized 5s2 to 5s15p1 electronic transitions of [SbCl6](3)- polyatomic anions. In comparison with the cubic double perovskite phosphor Cs2NaInCl6:Sb3+, the octahedral tilting distortion increases the electronic isolation of the In/Sb-centered octahedra thus facilitating electron and hole localization on Sb-3(+) sites, leading to bright photoluminescence. The distorted crystal structure also leads to a larger Stokes shift (1.29 eV) and a corresponding red shift of the emission peak (?max = 522 nm) compared to the more symmetric Cs2NaInCl6:Sb-3(+) (Stokes shift approximate to 0.94 eV, lambda(max) = 445 nm).