C-Dots and composites based on them face the challenges of poor stability, especially under photo-radiation, and low solid-state photoluminescence quantum yields (PLQYs), which hinder their application in optical devices. Herein, a novel 2-dimensional hybrid material of polysiloxane embedded with Si-doped carbon dots (P-E-Si-CDs) was synthesized by a self-assembly approach, and the hybrid composite exhibited broadband blue-green fluorescence emission, outstanding photostability, high thermal stability, and a high PLQY of 82.8%. Moreover, the dual fluorescent emissions were demonstrated the creation of two closed-loop fluorophores. Using the as-prepared hybrid fluorescent material, fabricated light-emitting diodes (LEDs) based on UV and blue-emitting LED chips present safe warm white light emission and adjustable white emission with a high color rendering index of up to 91, respectively. This work provides a novel strategy for the design and realization of Si-CD-based hybrid composites, thus promising their prospective use commercially in LED lighting.