The pseudobinary system LaLuO3–LaScO3 was explored in hopes of discovering new perovskite-type substrates with pseudocubic lattice parameters above 4Å. A complete solid solution of the type (LaLuO3)1−x(LaScO3)x forms between the end members LaLuO3 and LaScO3, enabling large single crystals of (LaLuO3)1−x(LaScO3)x to be grown from the melt. A single crystal with x≈0.34 was demonstrated. Considering the maximum thermal load of the iridium crucibles appropriate for Czochralski growth of this solid solution, the theoretically maximum achievable x-value is ~0.67. Based on the phase diagram determined, it is anticipated that single crystals with pseudocubic lattice constants between 4.09 and 4.18Å can be grown in this system by the Czochralski method.