An experimental technique based on frequency-resolved four-wave mixing is proposed for the investigation of phonon-assisted capture of electrons and holes in electrically pumped semiconductor quantum wells. We show how this technique can be used to directly measure the intrinsic capture lifetime, with no need for involved numerical fits. We also present experimental results from an application of the technique to a multiquantum-well semiconductor optical amplifier. The possible impact of phase matching on the results is discussed. ©1997 American Institute of Physics.