To improve the flame retardancy of polycarbonate (PC), a novel and environmentally friendly flame retardant was synthesized by combining boron-doped silicone resin (BSR) with a layered double hydroxide (LDH) modified with sodium dodecyl benzenesulfonate (SDBS) which was denoted as DBS-LDH/BSR. The structure of the hybrid was characterized by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS), which indicated that BSR was successfully combined with DBS-LDH. X-ray diffraction (XRD) studies showed that the reaction of BSR occurred only on the surface of DBS-LDH. In addition, scanning electron microscopy (SEM) was used to further verify the combination of DBS-LDH with BSR. PC exhibited the optimum flame retardancy following the incorporation of 10 wt% DBS-LDH/BSR (5 wt% DBS-LDH and 5 wt% BSR). Based on thermogravimetric analysis, the char residue of this PC composite in air at 750 °C increased to 3.60 wt%. Mechanical test showed that the DBS-LDH/BSR could affect the mechanical properties after incorporation into PC. According to the UL-94 vertical burning test, the flame retardant rating of the PC composite improved to V-0. Furthermore, the limiting oxygen index (LOI) value of the PC composite increased to 34%. According to the cone calorimeter test, the peak heat release rate (PHRR) dramatically decreased by 44%. The morphology of the PC composite after combustion was characterized by SEM, which revealed that the pores of the composite were smaller than those of pure PC. This result was attributed to the limited spread of oxygen and heat permeation. Thus, both DBS-LDH and BSR contributed to the synergistic effects of reducing the fire hazard of PC.