Ultrafast recombination of holes with shallow acceptors in a III-V semiconductor is directly observed for the first time, by means of picosecond infrared spectroscopy. Neutral impurities in p-doped GaAs at low temperature are photoionized by picosecond infrared excitation. The recombination of free holes with negatively charged acceptors-monitored via absorption changes below the band edge-occurs on a time scale of several tens of picoseconds, following a nonexponential kinetics. Emission of longitudinaloptical phonons by the free holes is found to be the dominant mechanism of recombination.PACS numbers: 71.55.Eq, 78.30.Fs The energy levels of shallow impurities in extrinsic semiconductors represent localized electronic states which strongly affect the optical and electrical properties of the material. Dipole-allowed transitions between the ground state of impurities and delocalized states in the valence and conduction bands result in distinct absorption and emission bands [1]. For charge transport at high electric fields, repeated scattering of carriers between continuum states and the excited levels of the impurities, i.e., carrier trapping and impurity ionization, reduces the conductivity of the material. Those processes are particularly relevant at low temperatures and high doping densities where a certain fraction of impurities is ionized [2].In the early cascade-capture model, carrier trapping is described as emission of a sequence of single acoustic phonons, followed by a final relaxation to the impurity ground state [3]. Refined theoretical treatments have been developed to account for multiple scattering and have calculated cross sections of carrier capture [2]. More recently, Monte Carlo techniques have been used to simulate the kinetics of charge transport [2,4]. Extensive experimental work has concentrated on stationary transport or electrical noise measurements giving capture cross sections for shallow donors and acceptors in silicon and germanium [5]. In contrast, very limited information exists on the microscopic dynamics of carrier capture. Nanosecond trapping times have been deduced from time-resolved transport studies on n-type germanium [6] and from the photo-Hall effect of p-type silicon [7]. In GaAs, time-resolved studies of impurity related luminescence report electron and hole capture on a time scale between 10 and 500 ns [8]. The observed relaxation rates are mainly determined by the interaction between free carriers of low kinetic energy and acoustic phonons [2]. In GaAs and other III-V semiconductors, the interaction with optical phonons is much stronger than the acoustic deformation potential. Thus enhanced capture rates should occur if electrons and holes have sufficient energy to emit longitudinal (LO) or transversal (TO) optical phonons. Furthermore, the large energy of the optical phonons compared to acoustic phonons allows the direct population of the ground state of a shallow impurity by emission of a single optical phonon if the phonon energy is higher than the ionization ene...