Very little is known about the realm of solid-state metal halide compounds comprising two or more halometalate anions. Such compounds would be of great interest if their optical and electronic properties could be rationally designed. Herein, we report a new example of metal halide cluster-assembled compound (C<sub>9</sub> NH<sub>20</sub> )<sub>9</sub> [Pb<sub>3</sub> Br<sub>11</sub> ](MnBr<sub>4</sub> )<sub>2</sub> , featuring distinctly different anionic polyhedra, namely, a rare lead halide cluster [Pb<sub>3</sub> Br<sub>11</sub> ]<sup>5-</sup> and [MnBr<sub>4</sub> ]<sup>2-</sup> . In accordance with its multinary zero-dimensional (0D) structure, this compound is found to contain two distinct emission centers, 565 nm and 528 nm, resulting from the formation of self-trapped excitons and <sup>4</sup> T<sub>1</sub> -<sup>6</sup> A<sub>1</sub> transition of Mn<sup>2+</sup> ions, respectively. Based on the high durability of (C<sub>9</sub> NH<sub>20</sub> )<sub>9</sub> [Pb<sub>3</sub> Br<sub>11</sub> ](MnBr<sub>4</sub> )<sub>2</sub> upon light and heat, as well as high photoluminescence quantum yield (PLQY) of 49.8 % under 450 nm blue light excitation, white light-emitting diodes (WLEDs) are fabricated, showcasing its potential in backlight application.