In this letter, we report an experimental realization of distributing entangled photon pairs over 100 km of dispersion-shifted fiber. In the experiment, we used a periodically poled lithium niobate waveguide to generate the time-energy entanglement and superconducting single-photon detectors to detect the photon pairs after 100 km. We also demonstrate that the distributed photon pairs can still be useful for quantum key distribution and other quantum communication tasks.