We have investigated photoluminescence (PL) at 4.2 K in highly doped and highly compensated Si with donor and acceptor impurities in the intermediate concentration range from 1 × 1016 to 3 × 1018 cm−3. PL spectra were dominated by the radiative recombination of excitons bound by impurity clusters and the donor–acceptor pair emission. The peak position of the exciton emission shifts to the lower energy side monotonically with an increase in the sum of the donor and acceptor concentrations, where the relationship between the position and the concentration is universal regardless of the species of impurities and is valid also for uncompensated Si. This allowed us to suggest that the cluster consists of multiple species of donor and acceptor impurities and that the difference in the species does not cause a detectable variation in the binding energy of an exciton. A possible method for quantifying the donor and acceptor impurities is proposed.