Experimental and theoretical research on the recombination photoluminescence of free hot electrons in semiconductors (primarily GaAs) is reviewed. The polarization characteristics are discussed. These characteristics reflect, in particular, a momentum alignment of the electrons by linearly polarized light and an effect of a ripple in the constant-energy surfaces in the valence band. The dependence of the linear polarization on the spectrum is discussed in connection with various mechanisms for the energy relaxation of the hot electrons. The depolarization of the hot-electron photoluminescence in a magnetic field is discussed. A procedure is discussed for determining the energy relaxation times and the scale times for intervalley transitions through an analysis of depolarization curves. The energy distribution of the hot electrons is found from the hot-electron photoluminescence spectrum. The recombination luminescence of hot holes is discussed. These holes appear when the semiconductor is illuminated in the spin-split-offsubband.