© 2019 Elsevier B.V. This work presents the structural characterisation of PbS nanofilms deposited by the chemical bath deposition technique at 70±2 °C using Polyethyleneimine, Triethanolamine and Ammonium nitrate as complexing agents, which allow a controlled and constant ion by ion reaction in aqueous medium whose chemical bath reactions take place in basic solutions with typical pH values 9–12, distinguishing the complexes obtained by their thermodynamic stability and kinetic stability. The PbS fundamental stretching frequencies were determined by Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy gives the relative atomic composition and identification of the most intense photoelectron transitions S2p (164 eV) and Pb4f 7/2 (137.34 eV) for the PbS-Nitrate film, which are associated with the Pb (II) oxidation state. The shift to higher binding energies, Pb4f7/2 (139.01 eV) for PbS-Polyethyleneimine and PbS-Triethanolamine show the presence of PbO2 with oxidation state Pb (IV). X-ray diffraction analysis and Raman spectroscopy reveal that PbS deposited nanofilms had pure cubic galena crystalline phase when ammonium nitrate was used as complexing agent, with the Polyethyleneimine complexing agent, the formation of cubic PbS in cubic phase with monoclinic Lanarkite Pb2(SO4)2 traces were observed. Finally, using Triethanolamine as complexing agent, cubic phase PbS with orthorhombic Anglesite and lead oxide (x∼1.57) traces were found. The surface morphology of the samples was obtained by High Resolution Transmission Electron Microscopy. The thin films show three direct band gaps, around 0.77–0.78 and 0.84–0.88 eV belonged to the mid-trap state caused by –Pb dangling bond and S+2 levels and the band gap energy at 0.91–1.10 eV was attributed to the quantum confinement associated to grain size, which were obtained by transmittance.