The physical understanding of the optical properties of dental biomaterials is mandatory for their final success in restorative applications. Light propagation in biological media is characterized by the absorption coefficient, the scattering coefficient, the scattering phase function, the refractive index, and the surface conditions (roughness). We have employed the inverse adding-doubling (IAD) method to combine transmittance and reflectance measurements performed using an integrating-sphere setup with the results of the previous scattering-anisotropy goniometric measurements. This has led to the determination of the absorption and the scattering coefficients. The aim was to optically characterize two different dental-resin composites (nanocomposite and hybrid) and one type of zirconia ceramic, and comparatively study them. The experimental procedure was conducted under repeatability conditions of measurement in order to determine the uncertainty associated to the optical properties of the biomaterials. Spectral variations of the refraction index and the scattering anisotropy factor were also considered. The whole experimental procedure fulfilled all the necessary requirements to provide optical-property values with lower associated uncertainties. The effective transport coefficient presented a similar spectral behavior for the two composites but completely different for the zirconia ceramic. The results demonstrated that the scattering anisotropy exerted a clearly distinct impact on the optical properties of the zirconia ceramic compared with those of the dental-resin composites.