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We report on a method for the simultaneous determination of refractive index profiles and mode indices from the measured near-field intensity profiles of optical waveguides. This method has been applied to UV-written single-mode optical waveguides in LiNbO3 for the optimization of the writing conditions. The results for the waveguides written with light of the wavelengths 275, 300.3, 302, and 305 nm for different writing powers and scan speeds reveal that for optimum writing conditions a maximum possible refractive index change of ~0.0026 can be achieved at a value of 632.8 nm transmitting wavelength. The computation process used in the presented technique may also become useful to extract absolute refractive index values of any slowly varying graded index waveguide.