Thin lead sulfide films were grown on single crystal GaAs(100) substrates by chemical deposition using Pb(NO3)2 and CS(NH2)2 with excess of NaOH in aqueous solution at a range of deposition temperatures 0–50 °C. The microstructure and morphology evolution were studied as a function of the deposition conditions, resulting in a wide range of microstructures. Ultrahigh resolution scanning electron microscopy and atomic force microscopy indicated a systematic change in particle shape and surface morphology as a function of deposition temperature and deposition time. X-ray diffraction of 200–500 nm thick films indicated a dominant $\langle 110\rangle$ texture throughout the deposition temperature range. At deposition temperatures above 40 °C, single crystal films were obtained. Cross-sectional transmission electron microscopy analyses showed a unique (011)PbS||(100)GaAs and [100]PbS||[011]GaAs orientation relationship.