Silica based nanofibres have been deposited on unglazed ceramic tiles by combining electrospinning and sol–gel processes. Poly(vinyl pyrrolidone) (PVP) alcoholic solutions and commercial spin on glass (Accuglass) mixtures have been used to obtain composite fibrous non-woven mats totally converted, after thermal annealing at 600 °C, to SiO2 microsphere “necklaces”. The possibility to get an uniform fibres coverage onto the tile surface confirms the validity of electrospinning (easily scalable to large surface samples) as coating strategy to cover the macroscopic defects typical of the polished unglazed tile surface and improve surface planarization.