Carbon nanotube (CNT)/SiO2 composite nanofibres were fabricated by electrospinning treated calcination under nitrogen atmosphere. To obtain CNT/SiO2 composite nanofibres, functionalised CNTs (fCNTs) were prepared by chemical oxidation and mixed with tetraethyl orthosilicate : H2O : H3PO4 : poly(vinyl alcohol) solutions. The resulting solutions were electrospun under adjusted parameters and the properties of the composite nanofibre solution were measured. The dispersity and direction of CNTs in the composite nanofibres were also monitored. By using fCNTs, the CNTs were well dispersed in CNT/SiO2 composite nanofibres by improving the dispersity of CNTs in the TEOS sol-gel/PVA solution. fCNTs can therefore be used to enhance the dispersity and direction of CNTs in SiO2 composite nanofibres prepared by electrospinning.