Carbon dots (CDs) are a new class of carbon nanomaterials and luminescent materials. Due to their fascinating properties, CDs can be widely applied in many fields, including bioimaging, biosensors, and photocatalysis. Performance characteristics of CDs are mainly concentrated in diluted solutions for a long time, it is possible to play advantages of small size effect and excellent cell permeability. However, the single morphology limits the development and applications cannot make progress further. To take full advantage of the low-toxicity, strong-luminescence CDs in the fields of biophotonics and optoelectronics, it is desirable to embed them in an appropriate solid matrix. Recently, due to its simplicity, versatility and cost-effectiveness, the electrospinning technique has been widely used to fabricate nanofibers from a wide variety of materials. To our knowledge, there are very few reports available on CDs embed in one-dimensional nanofibers. Herein, we use silane pre-functionalized CDs (SiCDs) and select silane as alkoxide precursor, then the SiCD/SiO2 composite nanofibers are prepared by combining sol-gel method with electrospinning technique. The resulting product may possess new physical or chemical properties from the two components. The fluorescence quantum yield of the SiCD/SiO2 composite nanofibers is as high as 90% and the fluorescence lifetime can reach up to about 6 ns. Bioapplication experiment confirm the low cytotoxicity, well bioimaging and biocompatibility of these nanofibers. It is expected that this one-dimensional composite fibers may have more wide applications in bioimaging, textile, and optical devices for their novel geometrical structure and luminescent properties.