We present a general bifurcation in the synchronized dynamics of time-delay-coupled nonlinear oscillators. The relative phase between the oscillators jumps from zero to pi as a function of the coupling; this phase-flip bifurcation is accompanied by a discontinuous change in the frequency of the synchronized oscillators. This phenomenon is of broad relevance, being observed in regimes of oscillator death as well as in periodic, quasiperiodic, and chaotic dynamics. Time-delay coupling is necessary for the phase-flip bifurcation. We illustrate the phenomenon, and present analytical results for paradigmatic nonlinear systems. Possible applications are discussed.