The metal halide perovskite have garnered significant attention for their exceptional photoelectric properties. However, their inherent instability and the sharp decrease of photoluminescence quantum yield (PLQY) in the solid-state significantly limit their practical applications. Appropriate heterojunction structures or matrix encapsulation can efficiently improve the PLQY and stability of the metal halide perovskite. Herein, we report a new silicon-based ligand hydrolysis condensation encapsulation to synthesize CsPbBr3/Cs4PbBr6/BTESPA-x (CPB–Si-x) composite powders with improved luminescence properties and enhanced thermal stability. With the increase of BTESPA (from 0 to 150 μL), the efficient hydrolysis condensation process occurs on the surface of CsPbBr3/Cs4PbBr6. Finally, the abundant amino-silane groups in BTESPA bind to undercoordinated Pb2+, thereby suppressing the surface defect states and enhancing the PLQY from 34.3 % for CsPbBr3/Cs4PbBr6 (CPB) to 82.1 % for CPB-Si-5. Simultaneously, the thermal stability of CPB-Si-5 exhibits a 13 % improvement over that of CPB after undergoing thermal cycling. Furthermore, tricolor white light-emitting-diode (WLEDs) with high color rendering index were fabricated using on-chip blue LED with bright green-emissive CPB-Si-5 composite powder and red-emissive K2SiF6:Mn4+ phosphor, demonstrating the potential applicability of these powders in WLED backlight systems.