Silicon carbide (SiC) has been considered a promising metal-free photocatalyst due to its unique photoelectrical properties and thermal/chemical stability. However, its performance suffers from the fast recombination of charge carriers. Herein, we report mesoporous SiC nanofibers with in situ embedded graphitic carbon (SiC NFs-Cx) synthesized via a one-step carbothermal reduction between electrospun carbon nanofibers and Si powders. In the absence of a noble metal co-catalyst, the hydrogen evolution efficiency of SiC NFs-Cx is significantly improved under both simulated solar light (180.2 μmol·g–1·h–1) and visible light irradiation (31.0 μmol·g–1·h–1) in high-pH solution. The efficient simultaneous separation of charge carriers plays a critical role in the high photocatalytic activity. The embedded carbon can swiftly transfer the photogenerated electrons and improve light absorption, whereas the additional hydroxyl anions (OH–) in highpH solution can accelerate the trapping of holes. Our results demonstrate that the production of SiC NFs-Cx, which contains exclusively earth-abundant elements, scaled up, and is environmentally friendly, has great potential for practical applications. This work may provide a new pathway for designing stable, lowcost, high efficiency, and co-catalyst-free photocatalysts.