We present the experimental demonstration of a new scheme for the generation of ultrashort pulse trains based on free-electron-laser (FEL) emission from a multipeaked electron energy distribution. Two electron beamlets with energy difference larger than the FEL parameter have been generated by illuminating the cathode with two ps-spaced laser pulses, followed by a rotation of the longitudinal phase space by velocity bunching in the linac. The resulting self-amplified spontaneous emission FEL radiation, measured through frequency-resolved optical gating diagnostics, reveals a double-peaked spectrum and a temporally modulated pulse structure. DOI: 10.1103/PhysRevLett.111.114802 PACS numbers: 41.60.Cr, 42.55.Àf, 42.65.Ky Radiation pulses with attosecond to femtosecond time scales represent a real possibility for a breakthrough in science and technology, permitting unprecedented insights into the ultrafast electron and nuclear dynamics [1][2][3]. The time-resolved study of electron rearrangements could lead to significant advances in the understanding of intermolecular processes, chemical bond breaking and formation, and the interaction of photoactivated molecules with their environment.Trains of ultrashort radiation pulses enable stroboscopic electron imaging [4] and the investigation of the response accompanying collective electron motion in nanomaterials [5]. They also find further applications in other technical fields, such as the enhancement of transmission or reflectivity in materials, resonant inelastic x-ray scattering, or the ab initio phasing of nanocrystals [6].Sequences of spikes have been synthesized by means of the high harmonic generation driven by lasers in gases [7] and regularly used in experiments [4,8], but are severely limited in efficiency approaching the keV range.Free-electron lasers (FELs) are capable of producing high brightness pulses in the x-ray spectral region [9][10][11][12]. The FEL, in the self-amplified spontaneous emission (SASE) mode of operation [13], generates radiation with limited temporal coherence [14], time duration of the order of the electron bunch length and structured in a chaotic succession of random peaks. The typical time scale of these radiation spikes is set by the FEL Pierce parameter [13]. Several techniques have been explored to increase longitudinal coherence, stability, and/or to shorten the FEL pulse time scale towards the attosecond domain. The amplification of one single SASE spike has been demonstrated by compressing the electron beam close or below the FEL coherence length [15,16], by using a chirped bunch energy combined with a matched undulator taper [17][18][19], or by spoiling the whole electron beam except a limited fraction [20,21], a technique that has also been implemented to produce double pulse two-color radiation for pump and probe experiments [22]. Short single or multiple pulses have also been produced in seeded or cascaded FELs [23][24][25][26][27], with increased coherence and shot to shot stability. More sophisticated seeding concept...