Transition metal dichalcogenides (TMDs) have shown outstanding semiconducting properties which make them promising materials for next-generation optoelectronic and electronic devices. These properties are imparted by fundamental carrier–carrier and carrier–phonon interactions that are foundational to hot carrier cooling. Recent transient absorption studies have reported ultrafast time scales for carrier cooling in TMDs that can be slowed at high excitation densities via a hot-phonon bottleneck (HPB) and discussed these findings in the light of optoelectronic applications. However, quantitative descriptions of the HPB in TMDs, including details of the electron–lattice coupling and how cooling is affected by the redistribution of energy between carriers, are still lacking. Here, we use femtosecond pump–push–probe spectroscopy as a single approach to systematically characterize the scattering of hot carriers with optical phonons, cold carriers, and defects in a benchmark TMD monolayer of polycrystalline WS2. By controlling the interband pump and intraband push excitations, we observe, in real-time (i) an extremely rapid “intrinsic” cooling rate of ∼18 ± 2.7 eV/ps, which can be slowed with increasing hot carrier density, (ii) the deprecation of this HPB at elevated cold carrier densities, exposing a previously undisclosed role of the carrier–carrier interactions in mediating cooling, and (iii) the interception of high energy hot carriers on the subpicosecond time scale by lattice defects, which may account for the lower photoluminescence yield of TMDs when excited above band gap.