Knowledge about the working mechanism of the PbS:P3HT:PCBM [P3HT=poly(3-hexylthiophene), PCBM=[6,6]-phenyl-C-61 -butyric acid methyl ester] hybrid blend used for efficient near-infrared photodiodes is obtained from time-resolved photoluminescence (PL) studies. To understand the role of each component in the heterojunction, the PL dynamics of the ternary (PbS:P3HT:PCBM) blend and the binary (PbS:P3HT, PbS:PCBM and P3HT:PCBM) blends are compared with the PL of the pristine PbS nanocrystals (NCs) and P3HT. In the ternary blend the efficiency of the charge transfer is significantly enhanced compared to the one of PbS:P3HT and PbS:PCBM blends, indicating that both hole and electron transfer from excited NCs to the polymer and fullerene occur. The hole transfer towards the P3HT determines the equilibration of their population in the NCs after the electron transfer towards PCBM, allowing their re-excitation and new charge transfer process.