By using a novel and low-cost microwave method, three-dimensional SiC networks have been synthesized in large-scale. The composition and structural features of the product were characterized by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. The results show that the SiC networks consist of nanocable X-junction and Y-junction. Some nanocables are composed of 3C–SiC multicore encapsulated in single amorphous SiO2 shell. The SiC networks emitted stable violet–blue light around 380 nm under 325-nm excitation. Compared to the emission peak of the SiC networks after etched and the reported results of 3C–SiC nanowires, the emission peak of the SiC networks shows significant blueshift. The origin of the photoluminescence for the SiC networks could be due to two possible reasons: the central crystalline SiC nanowires and amorphous SiO2 shell. A two-step growth mechanism of the SiC networks was proposed based on the experimental characterizations. The successful synthesis of SiC networks is an important step in the development of SiC-based electronic devices and circuits.