The commercial viability of fluorescent materials is critically contingent on their thermal stability. Recent interest has converged on lead-free double perovskites (DPs), renowned for their optical properties mirroring those of traditional lead-based counterparts and superior atmospheric stability. However, these materials encounter significant fluorescence degradation in thermal environments, a challenging scenario given the high temperatures endemic to the surfaces of optoelectronic devices during prolonged operation, detrimentally impacting the fluorescent attributes of lead-free DPs. To address this challenge, in situ synthesis of lead-free DP nanocrystals (NCs) within KIT-6 mesoporous molecular sieves is proposed, yielding Cs2AgIn0.98Bi0.02Cl6@KIT-6 NCs with enhanced optical qualities. Experimental results demonstrate a marked enhancement in the fluorescence thermal stability of these NCs, attributed to the protective KIT-6 shell layer. Subjected to high power operation (100 mA) for 270 minutes, the fabricated orange light-emitting diode (LED) device maintained 80% of initial luminous efficiency, despite the resultant elevated surface temperature of 326.8 K. Therefore, this novel in situ assembly approach significantly bolsters the operational stability of lead-free DPs, paving the way for their potential commercial applications. © 2024 The Royal Society of Chemistry.