We have studied Cu2S absorber layers prepared by physical vapor deposition (PVD) by calibrated spectral photoluminescence (PL) and by confocal PL as function of temperature T and excitation fluxes to obtain the absolute PL-yield at an excitation flux equivalent to the AM1.5 spectrum and to calculate the splitting of the quasi-Fermi levels (QFL) µ = Ef,n-Ef,p and the absorption coefficient α(E), both in the temperature range 20 K ≤ T ≤ 400 K. The PL-spectra reveal two peaks at E1 = 1.17 eV and E2 = 1.3 eV, of which the low energy peak is only detectable at temperatures T < 200 K. The samples show an impressive QFL-splitting of µ > 700 meV at 300 K associated with a pseudo band gap of Eg = 1.25 eV. The high energy peak shows an unexpected temperature behavior, namely an increase of the PL-yield with rising temperature at variance with the behavior of QFL-splitting that decreases with rising T from extrapolated T = 0K value of µ = 1.3 eV. The PL-yield versus temperature will be discussed in terms of different defect states in the band gap. Our observations indicate that, contrary to common believe, it is not the PL-yield, but rather the QFL-splitting that is the comprehensive indicator of the quality of the excited state in an illuminated semiconductor. A further examination of the lateral variation of the opto-electronic properties by confocal PL shows a strong correlation between the QFL-splitting, the Urbach energy EU and the optical band gap Eopt, respectively.