We report the first observation of piezoelectricity and ferroelectricity in individual Sb2S3 nanowires embedded in anodic alumina templates. Switching spectroscopy piezoresponse force microscopy (SS-PFM) measurements demonstrate that individual, c-axis-oriented Sb2S3 nanowires exhibit ferroelectric as well as piezoelectric switching behavior. Sb2S3 nanowires with nominal diameters of 200 and 100 nm showed d33(eff) values around 2 pm V−1, while the piezo coefficient obtained for 50 nm diameter nanowires was relatively low at around 0.8 pm V−1. A spontaneous polarization (Ps) of approximately 1.8 μC cm−2 was observed in the 200 and 100 nm Sb2S3 nanowires, which is a 100% enhancement when compared to bulk Sb2S3 and is probably due to the defect-free, single-crystalline nature of the nanowires synthesized. The 180° ferroelectric monodomains observed in Sb2S3 nanowires were due to uniform polarization alignment along the polar c-axis.