In this Letter we study the evolution of an initial periodic modulation in the temporal profile of a relativistic electron beam under the effect of longitudinal space-charge forces. Linear theory predicts a periodic exchange of the modulation between the density and the energy profiles at the beam plasma frequency. For large enough initial modulations, wave breaking occurs after 1/2 period of plasma oscillation leading to the formation of short current spikes. We confirm this effect by direct measurements on a ps-modulated electron beam from an rf photoinjector. These results are useful for the generation of intense electron pulse trains for advanced accelerator applications.