Silica nanorods were successfully prepared through a sol-gel process in the presence of carboxylic-functionalized single-walled carbon nanotubes (C-SWCNTs). The effect of chemical functionalization of single-walled carbon nanotubes (SWCNTs) on the growth of the silica layer was investigated using pristine SWCNTs (P-SWCNTs) and C-SWCNTS. The C-SWCNTs served as a unique template to fabricate silica hybrid composite materials. The crystalline formation and growing mechanism of the silica layer on C-SWCNTs were explained by the hydrolysis and chemical bonding between silica precursors and carboxylated SWCNTs. The C-SWCNTs, as templates, were successfully encapsulated using silica, and used templates were removed by oxidation at high temperature. Finally, silica nanorods/nanowires were synthesized in forms of mold, and this silica fabrication mechanism could be applied for large-scale production of silica nanomaterials and highly flexible nanocomposites. The sequence of a silica encapsulation process of C-SWCNTs and removed C-SWCNTs was characterized using SEM, TEM, EDX, FT-IR and Raman spectroscopy, XRD, and electrical analysis.