We investigate the effect of TiCl4 treatment on the refractive index of a nanoporous TiO2 film. A nanoparticulate TiO2 film prepared on a glass substrate was immersed in a TiCl4 aqueous solution. The subsequent reaction of TiCl4 with H2O produces TiO2 and thus modifies the density and the refractive index of the film. With increasing TiCl4 concentration, the refractive index initially increased and then declined after being maximized (n = 2.02 at 633 nm) at 0.08 M concentration. A refractive index change as large as 0.45 could be obtained with the TiCl4 treatment, making it possible to achieve diffraction efficiency exceeding 80% in a diffraction grating-embedded TiO2 film. For high TiCl4 concentrations of 0.32 M and 0.64 M, the refractive index remained nearly unchanged. This was attributed to the limited permeability of high-viscosity TiCl4 solutions into the nanoporous films. The measured pore size distributions were in good agreement with the results of a diffraction analysis and refractive index measurement. (C) 2015 Elsevier B.V. All rights reserved.