During the last decade, solution-processed colloidal quantum dots (CQDs) have attracted significant attention for low-cost fabrication of optoelectronic devices. In this study, lead sulfide (PbS) CQDs were synthesized via the hot injection method and the effect of doping elements with low electron affinity, including cadmium, calcium and zinc, on the passivation of trap states was investigated. A red-shift in the luminescence emission was observed by doping through passivation of lead dangling bonds. Time-resolved photoluminescence measurements showed that the lifetime of charged carriers was significantly enhanced by cadmium doping (∼80%) which is quite noticeable compared with calcium- and zinc-doped nanocrystals. External quantum efficiency measurements on thin solid films (∼300 nm) prepared by spin coating supported improved lifetime of carriers through passivation of mid-gap trap states. In order to show the potential application of the doping process, bulk heterojunction CQD solar cells were fabricated. It was found that the power conversion efficiency (PCE) was improved up to ∼40%; the highest improvement was observed with the Cd treatment. Finally, density functional theory (DFT) and electrochemical impedance spectroscopy (EIS) were employed to study the effect of doping on the density of states. The results showed that doping with low electron affinity metals effectively reduced the deep trap states of PbS QDs.