Reactive magnetron sputtering deposition processes based on rotating or double cathodes allow the deposition of multiple TiO2//SiO2 layers on glass for obtaining antireflective coatings for large area applications with a good homogeneity and high resistance against environmental attacks. By increasing the number of TiO2//SiO2 layers, the luminous reflectance of the coated glass decreases but the calculation of angular daylight and energy parameters requires the use of an increasing number of complementary analytical techniques due to the complexity of the coating. In this paper we show how Rutherford back-scattering, neutron reflectivity and spectrophotometry can be successfully utilised to perform a quite complete characterisation of commercial antireflective coatings based on three TiO2//SiO2 layers.