In this study we apply time resolved photoluminescence and contactless electroreflectance to study the carrier collection efficiency of a GaInNAsSb/GaAs quantum well (QW). We show that the enhancement of photoluminescence from GaInNAsSb quantum wells annealed at different temperatures originates not only from (i) the improvement of the optical quality of the GaInNAsSb material (i.e., removal of point defects, which are the source of nonradiative recombination) but it is also affected by (ii) the improvement of carrier collection by the QW region. The total PL efficiency is the product of these two factors, for which the optimal annealing temperatures are found to be ~700 °C and ~760 °C, respectively, whereas the optimal annealing temperature for the integrated PL intensity is found to be between the two temperatures and equals ~720 °C. We connect the variation of the carrier collection efficiency with the modification of the band bending conditions in the investigated structure due to the Fermi level shift in the GaInNAsSb layer after annealing.