[en] We report on the first observation of the decay K_L→π⁰e⁺e^- γ by the KTeV E799 experiment at Fermilab. Based upon a sample of 48events with an estimated background of 3.6±1.1 events, we measure the K_L→π⁰e⁺e^- γ branching ratio to be (2.34±0.35±0.13) x 10^-8 . Our data agree with recent O(p⁶) calculations in chiral perturbation theory that include contributions from vector meson exchange through the parameter a_V . A fit was made to the K_L→π⁰e⁺e^- γ data for a_V with the result -0.67±0.21±0.12 , which is consistent with previous results from KTeV