Abstract PbS colloidal quantum dot solar cells (CQDSCs) employ ZnO electron transport layer have achieved high efficiency. However, there is nearly no efficient and batch production method to balance the charge separation and recombination within the device, which is one of the most obviously barrier to a satisfactory conversion efficiency. Here, a n+-n double-layered ZnO electron transport layer (DETL) is prepared by a facile one-step magnetron sputtering under different Ar pressure, and employed in heterojunction PbS colloidal quantum dot solar cells (CQDSCs) for the purpose of increasing charge separation at heterojunction interface via energy-band alignment modulation. The ZnO DETL, composed of a 100-nm-thick n+-ZnO bottom layer (n = 8 × 1019 cm−3) and a 20-nm-thick n-ZnO top layer (n = 3 × 1016 cm−3) significantly improve the power conversion efficiency (PCE) of the CQDSCs by a factor of ~35% compared to the device with single-layered n- ZnO. Open-circuit photovoltage decay (OCVD) measurements prove that the graded energy alignment of ZnO DETL effectively reduces both interfacial and trapping-assisted charge recombination, relative to the single-layered ZnO. The facile Ar-pressure tuning method makes the energy-band alignment process more convenient and sheds a light on the application of DETL electrons transport layer, fabricated by the universal technique of magnetron sputtering.