Defining Time-Zero When a high-energy photon hits an atom and is absorbed, the result can be the excitation and emission of an electron. This photoemission, or photoelectric effect, is generally assumed to occur instantaneously, and represents the definition of “time-zero” in clocking such ultrafast events. Schultze et al. (p. 1658 , see the cover; see the Perspective by van der Hart ) use ultrafast spectroscopy, with light pulses on the time scale of several tens of attoseconds, to test this assumption directly. They excite neon atoms with 100 eV photons and find that there is a small (20-attosecond) time delay between the emission of electrons from the 2 s and 2 p orbitals of the atoms. These results should have implications in modeling electron dynamics occurring on ultrafast time scales.