We have observed that the amount of positronium (Ps) emitted from the surface of p-Si(100) is substantially increased if the sample is irradiated with 532 nm laser light just prior to the implantation of positrons. The energy of the emitted Ps has a constant value of ∼0.16 eV and is independent of the Si temperature and the applied laser fluence, while the photoemission yield depends on both of these parameters. These observations are consistent with Ps production via a previously observed excitonlike positron surface state that is populated in response to the production of electron-hole pairs in the Si. Possible applications of Ps photoemission include probing surface electron dynamics on Si, the generation of ultrashort Ps or positron pulses using ps lasers, and efficient production of Ps in cryogenic environments.