Triboelectric nanogenerators (TENGs) have drawn essential interest as highly sensitive sensors that can function efficiently in harsh conditions, which can be life‐saving but challenging to accomplish. Herein, this work explores carbon fiber (CF)‐reinforced liquid crystalline thermosetting (LCT) triboelectric composites as flame retardant triboelectric nanogenerators (FR‐TENGs). FR‐TENGs with controlled structural and chemical properties exhibit not only outstanding flame resistance but also excellent triboelectric performance and can be utilized in the oil drilling industry and space applications under extreme temperatures. This FR‐TENG is incombustible even after 60 s of trying, where most traditional triboelectric materials were burnt completely under similar conditions. The self‐powered FR‐TENG exhibits high thermal resistance and strong mechanical strength and generates Voc (125.7 V), Qsc (14 nC), and Isc (0.8 µA) as electrical performances. In addition, the developed carbon fiber reinforced liquid crystalline thermosetting (LCT‐2@BCF) composite also poses a shape memory effect (SME), which can be employed for early fire alarm sensors. This work manifests the bright prospect of applying CF/LCT composites in fields that require light weight, high strength, high temperature resistance, and flame retardancy.