Meso/microporous titania/silica/carbon (TSC) nanocomposites were synthesized through a one-pot soft template (P123) sol–gel method using furfuryl alcohol (FA) as a polymerizable carbon source. The only crystalline phase detected in the TSC gel was anatase TiO2, with a grain size of 5–7 nm. The surface area (23–397 m2/g), average pore size (2.6–7 nm) and pore volume (0.05–0.27 cm3 g−1) of the TSC composites could be tuned by adjusting the silica/titania, surfactant/oxide and FA/oxide molar ratios. Carbon-rich spherical regions were formed due to the poly-furfuryl alcohol (PFA) phase separation. The size of the carbon-rich spheres could be controlled by changing chemical compositions accordingly. Furthermore, the causes of PFA phase separation in the Ti–Si–C–O system were elucidated.