Sb2S3 thin films were deposited with various thickness on glass and flexible polymer Polyetherimide (PEI) substrates by simple chemical bath deposition. X-ray diffraction patterns reveal the formation of polycrystalline films with orthorhombic structure. The Sb2S3 thin films grown on the PEI substrate are rougher. The enhancement of roughness for Sb2S3/PEI thin films leads to improve their hydrophobic character. Furthermore, they show high values of contact angle (CA) around 162°. The absorption coefficient of thin films is determined to be higher than 104 cm−1. The band-gap energy has been found to be between 1.6 and 2.1 eV as a function of thickness which related to the variation of structural defects. Thus, the growth of these films significantly depends on the nature of the substrate and its thickness. The obtained results show that all Sb2S3 on glass and PEI thin films have potential applications in the self-cleaning windows and solar cells.