In the present work, for the first time, we reported the exploration of mesoporous 3C-SiC hollow fibers via single-spinneret electrospinning of polyureasilazane (PSN) and polyvinylpyrrolidone (PVP) solution followed by high-temperature pyrolysis treatment. The resultant products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM) and N2 adsorption. The as-prepared hollow fibers with totally mesoporous walls were uniformly sized in diameter and high purity in morphology. They were composed of single-crystalline 3C-SiC nanoparticles with a surface area of 21.75 m2/g and average pore diameter of ~34 nm. The PSN concentration played a determined role on the formation of hollow fibers rather than the conventional solid counterparts, enabling their growth in a tunable manner. A possible mechanism was proposed for the formation of mesoporous SiC hollow fiber.