The halide perovskite CsPbBr3 has shown its promise for green lightemitting diodes. The optimal conditions of photoluminescence and the underlying photophysics, however, remain controversial. To address the inconsistency seen in the previous reports and to offer high-quality luminescent materials that can be readily integrated into functional devices with layered architecture, we created thin films of CsPbBr3/Cs4PbBr6 composites based on a dual-source vapor-deposition method. With the capability of tuning the material composition in a broad range, CsPbBr3 is identified as the only light emitter in the composites. Interestingly, the presence of the photoluminescenceinactive Cs4PbBr6 can significantly enhance the light emitting efficiency of the composites. The unique negative thermal quenching observed near the liquid nitrogen temperature indicates that a type of shallow state generated at the CsPbBr3/Cs4PbBr6 interfaces is responsible for the enhancement of photoluminescence.