Hot electrons and phonons excited in GaAs by subpicosecond laser pulses have been studied by inelastic light scattering for photoexcited electron densities varying between 1017 and 1019cm−3. Transient overshoot of longitudinal-optical (LO) phonon temperature above the electron temperature has been observed. This is explained by the fast production of zone-center LO phonons by hot electrons combined with slower reabsorption of the emitted phonons due to rapid cooling of Γ valley electrons by intervalley scattering.