A comparison of three copper(I) compounds [1, Cu(dppb)(pz2Bph2); 2, Cu(pop)(pz2Bph2); 3, Cu(dmp)(phanephos)(+)] that show pronounced thermally activated delayed fluorescence (TADF) at ambient temperature demonstrates a wide diversity of emission behavior. In this study, we focus on compound 1. A computational density functional theory (DFT)/time-dependent DFT approach allows us to predict detailed photophysical properties, while experimental emission studies over a wide temperature range down to T = 1.5 K lead to better insight into the electronic structures even with respect to spin-orbit coupling efficiencies, radiative rates, and zero-field splitting of the triplet state. All three compounds, with emission quantum yields higher than ϕPL = 70%, are potentially well suited as emitters for organic light-emitting diodes (OLEDs) based on the singlet-harvesting mechanism. Interestingly, compound 1 is by far the most attractive one because of a very small energy separation between the lowest excited singlet S1 and triplet T1 state of ΔE(S1-T1) = 370 cm(-1) (46 meV). Such a small value has not been reported so far. It is responsible for the very short decay time of τ(TADF, 300 K) = 3.3 μs. Hence, if focused on the requirements of a short TADF decay time for reduction of the saturation effects in OLEDs, copper(I) complexes are well comparable or even slightly better than the best purely organic TADF emitters.