The design and optimization of light-based analytical devices often require optical characterization of materials involved in their construction. With the aim of benefiting lab-on-a-chip applications, a transmission spectrometric method for determining refractive indices, n, of transparent solids is presented here. Angular dependence of the reflection coefficient between material-air interfaces constitutes the basis of the procedure. Firstly, the method is studied via simulation, using a theoretical algorithm that describes the light propagation through the sample slide, to assess the potentially attainable accuracy. Simulations also serve to specify the angles at which measurements should be taken. Secondly, a visible light source and an optical fiber spectrometer are used to perform measurements on three commonly used materials in optical lab-on-a-chip devices. A nonlinear regression subroutine fits experimental data to the proposed theoretical model and is used to obtain n. Because the attainable precision using this method of refractive index determination is dictated by the uncertainty in the transmission measurements, the precision (with 95% confidence) for mechanically rigid samples, namely glass and poly(methyl methacrylate) (PMMA), is higher than those estimated for the elastomer sample (in-house-molded poly(dimethylsiloxane) (PDMS)). At wavelengths with the highest signal-to-noise ratio for the spectrometer setup, the estimated refractive indices were 1.43+/-0.05 (580 nm) for PDMS, 1.54+/-0.02 (546 nm) for glass, and 1.485+/-0.005 (656 nm) for PMMA. Accurate refractive index estimations with an average precision equal to 0.01 refractive index units (RIU) were obtained for PMMA and glass samples, and an average precision of 0.09 RIU for the PDMS molded slide between 550 and 750 nm was obtained.