AbstractGraphene is considered one of the most prominent halogen‐free multifunctional flame retardants for polymers, and the resultant nanocomposites also display a good balance of properties. However, the biggest concern nowadays is thermal oxidative degradation, which mainly affects the flame retardant (FR) efficiency of graphene. To improve the flame retardancy and thermal oxidative degradation efficiency, graphene was functionalized with a combination of polycyclotriphosphazes and siloxanes via a sol–gel surface modification method, yielding a graphene‐based hybrid FR (PSGO) containing multiple elements (P, N, S, and Si). The PSGO‐containing PA6 composite exhibited significant improvements in the water resistance, thermal, mechanical, and FR properties, as compared with those of 3‐isocyanatopropyltriethoxysilane functionalized graphene oxide (ITS‐GO) and siloxane‐modified polycyclotriphosphazenes (m‐PZS) individually. The peak heat release rate and total heat release values of the PA6 composites with 10 wt% PSGO decreased by 45.7% and 36.9%, respectively, compared to those of pristine PA6. Moreover, it was confirmed that 10 wt% PSGO in the PA6 composite resulting in a V–0 rating in the UL‐94 tests, even after the water immersion test. These attractive properties are attributed to the resistance to thermal‐oxidative degradation of PSGO and the improved interfacial interactions with the polymer matrix. Therefore, this PSGO can be used as a multifunctional modifier to improve the water resistance, thermal, mechanical, and FR properties of polymers.