High-temperature electronic materials are in constant demand as the required operational range for various industries increases. Here we design (A,A )B 2 O 6 perovskite oxides with [111] "rock salt" A-site cation order and predict them to be potential high-temperature piezoelectric materials. By selecting bulk perovskites which have a tendency towards only out-of-phase BO 6 rotations, we avoid possible staggered ferroelectric to paraelectric phase transitions while also retaining noncentrosymmetric crystal structures necessary for ferro-and piezoelectricity. Using density functional theory calculations, we show that (La,Pr)Al 2 O 6 and (Ce,Pr)Al 2 O 6 display spontaneous polarizations in their polar ground state structures; we also compute the dielectric and piezoelectric constants for each phase. Additionally, we predict the critical phase transition temperatures for each material from first-principles to demonstrate that the piezoelectric responses, which are comparable to traditional lead-free piezoelectrics, should persist to high temperature. These features make the rock salt A-site-ordered aluminates candidates for high-temperature sensors, actuators, or other electronic devices.