Flexible photoelectric devices are emerging as a new class of photovoltaic cells. In this study, lead (Pb) foil was used as a flexible substrate to grow in situ lead sulfide (PbS) film with good uniformity and adhesion by a solvothermal elemental direct reaction, resulting in a PbS/Pb Schottky junction formed naturally between the PbS film and underlying Pb foil. We found that the photocurrent response of the photoelectrochemical (PEC) cell was greatly improved through a facile oxygen (O2)-modulation-based post-processing technique. O2 could decompose the organic residue and oxidize the Pb at the interface between the PbS film and Pb foils. Different characterization techniques, including thermogravimetric analysis, differential scanning calorimetry, x-ray diffraction, energy-dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, the change in transient photocurrent density (J p) with time (t), dark current-voltage (I-V) and absorption spectra were applied to get a full understanding of the O2 modulation effect. The oxidization treatment of the PbS film could regulate the flow of charge carriers to reduce their recombination, leading to photoresponse enhancement for the PEC cells. In particular, the process could modulate the tunneling current and interface states to optimize dark I-V characteristics. In addition, the magnitude of the barrier height can be tuned by O2 modulation, which was explained by theoretical analysis and calculation. We also demonstrated that the in situ formed PbS film has outstanding adhesion on the flexible Pb substrate. Our film synthesis method and post O2-modulation design as well as the corresponding device assembly may provide a novel perspective to the flexible PCE-cell-related research.