The preparation of cerium-substituted barium lutetium borate, Ba2Lu5B5O17:Ce3+, is achieved using high temperature solid state synthesis. This compound crystallizes in the Ba2Y5B5O17-type structure and shows an efficient blue emission (lambda(max) = 447 nm) when excited by UV-light (lambda(ex) = 340 nm) with a photoluminescent quantum yield near 90%, a fast luminescence decay time (<40 ns), and a thermal quenching temperature of 452 K. Further, preparing a solid solution following Ba-2(Y1-xLux)(5)B5O17:Ce3+ (x = 0, 0.25, 0.50, 0.75, 1) confirms that all compounds are isostructural and follow Vegard's law. Substituting Y3+ for Lu3+ yields a nearly constant emission spectrum that blue-shifts by only 9 nm and has a consistent luminescence lifetime across the range prepared. The photoluminescent quantum yield (PLQY) and thermal quenching (T-50) of the solid solution, however, are dramatically impacted by the composition, with the PLQY decreasing to and the T-50 chopping 49 K going from x = 1 to x = 0. These significant changes in the optical properties likely stem from enhanced structural rigidity as the larger, more polarizable Y3+ is substituted for the smaller, harder Lu3+ cation. These results highlight the importance of optimizing chemical bonding to improve a phosphor's optical properties.