The optical properties of a variety of materials have been calculated using a recently developed ab initio method based on solving the Bethe-Salpeter equation of the two-particle Green's functions. Relevant self-energy and electron-hole interaction effects are included from first-principles. Results on selected semiconductors, insulators, surfaces, and conjugated polymers are discussed. In many of these systems, excitonic effects are shown to dramatically alter the excitation energies and the optical spectra.