SiO2/TiO2 optical thin films with variable compositions have been prepared by ion beam induced and plasma enhanced chemical vapour deposition (IBICVD and PECVD). While the films obtained by IBICVD were very compact, the PECVD ones with a high content of Ti presented a columnar microstructure. The formation of Si-O-Ti bonds and a change in the environment around titanium from four- to six-coordinated has been proved by vibrational and X-ray absorption spectroscopies. The refractive index increased with the titanium content from 1.45 to 2.46 or 2.09 for, respectively, the IBICVD and PECVD films. Meanwhile, the band gap decreased, first sharply and then more smoothly up to the value of pure TiO2. It is concluded that the optical properties of SiO2/TiO2 thin films can be properly tailored by using these two procedures. (c) 2005 Elsevier B.V. All rights reserved.