Ultrahigh-power terahertz (THz) radiation sources are essential for many applications, for example, THz-wave-based compact accelerators and THz control over matter. However, to date none of the THz sources reported, whether based upon large-scale accelerators or high-power lasers, have produced THz pulses with energies above the millijoule (mJ) level. Here, we report a substantial increase in THz pulse energy, as high as tens of mJ, generated by a high-intensity, picosecond laser pulse irradiating a metal foil. A further up-scaling of THz energy by a factor of ∼4 is observed when introducing preplasmas at the target-rear side. Experimental measurements and theoretical models identify the dominant THz generation mechanism to be coherent transition radiation, induced by the laser-accelerated energetic electron bunch escaping the target. Observation of THz-field-induced carrier multiplication in high-resistivity silicon is presented as a proof-of-concept application demonstration. Such an extremely high THz energy not only triggers various nonlinear dynamics in matter, but also opens up the research era of relativistic THz optics.