We present a study of the temporal decay of photoluminescence (PL) as detected by picosecond excitation correlation spectroscopy (PECS). We analyze the correlation signal that is obtained from two simple models; one where radiative recombination dominates, the other where trapping processes dominate. It is found that radiative recombination alone does not lead to a correlation signal. Parallel trapping type processes are found to be required to see a signal. To illustrate this technique, we examine the temporal decay of the PL signal for In-alloyed, semi-insulating GaAs substrates. We find that the PL signal indicates a carrier lifetime of roughly 100 ps, for excitation densities of 1×1016–5×1017 cm−3. PECS is shown to be an easy technique to measure the ultrafast temporal behavior of PL processes because it requires no ultrafast photon detection. It is particularly well suited to measuring carrier lifetimes.