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To investigate the metal oxide thin film application in optoelectronic field via changing its conduction type, the p–n junction with Bi-doped p-type ZnO and n-type MoS2 is fabricated by pulsed laser deposition. In this work, we explore the photovoltaic effect of the ZnO/MoS2 heterostructure, focusing on the function of tuning Bi contents in enhancing the photoelectric conversion efficiency. Doping-Bi ZnO thin film perfectly shows stable p-type semiconductor properties with high carrier concentration (about from 1 × 1016 to 1 × 1017 cm−3), high rational mobility (363 cm−2 V−1 s−1) and low resistivity (216.7 Ω). In addition, MoS2 clearly exhibits large quantities of nanosheets and distinct vertically standing structure. The power conversion efficiency (PCE) of ZnO:Bix/MoS2 enhances from 0.518% to 2.430% along with increasing doping Bi element from 1% to 7%, but when doping Bi content reaches 10%, the PCE decrease 0.552%. Essentially, the ability of capturing photon-generated carriers in ZnO:Bix film gradually increases as doping Bi content to without excessive doping content. These findings illustrate that this proposed Bi-doped ZnO has potential in promoting the photoelectric conversion efficiency of MoS2 based p–n junction. [ABSTRACT FROM AUTHOR]