Raman spectra and fluorescence of BaTiO3 and silica microspheres of different sizes have been studied. The observed whispering gallery modes (WGMs) have been assigned using theoretical simulations based on the Lorenz–Mie theory. The WGMs are found to have selective enhancements in the Raman spectra. The variations in the Raman spectra with the radial position of the excitation spot and excitation wavelength have been correlated with the morphology-dependent internal field distributions of the microspheres. The effect of a thin dye coating on the fluorescence and Raman spectra was studied, and a coating thickness of ∼200 nm was estimated from the theoretical simulation of experimentally observed data based on the Aden and Kerker theory. Copyright © 2011 John Wiley & Sons, Ltd.