Tin disulfide (SnS ) is a binary chalcogenide semiconductor having applications in solar cells, energy storage, and optoelectronics. SnS thin films were deposited by spraying the nanocolloids synthesized by pulsed laser ablation in liquid. The structure, morphology, and optoelectronic properties were studied for films obtained from two liquid media (ethanol and isopropanol) and after heat treatments at various temperatures. X-ray diffraction analysis confirmed the hexagonal crystal structure of the films, whereas the 2-H polytype structure was identified by micro-Raman spectroscopy. Oxidation states of Sn (4+) and S (2-) identified from high resolution X-ray photoelectron spectra confirmed the composition and chemical states of the films. The SnS thin films exhibited distinct porous surface morphologies as the liquid medium in laser ablation was varied. All as-prepared and annealed films showed photoluminescence with a high intensity peak at 485 nm and a low intensity peak at 545 nm. Thin films annealed at 300 °C showed improved electrochemical properties upon illumination using a blue LED light source. Current-voltage curves recorded in dark and light as well as the photoresponse measurements showed their suitability for utilization in optoelectronic devices. The results of this study may trigger further research towards fabrication of nanostructured thin films in large area for optoelectronic and photoelectrochemical applications in an environment friendly and cost-effective way.