Tin sulfide has been widely studied as electrode materials for supercapacitors owing to their high theoretical pseudocapacitance. This paper reports a novel green synthesis of tin sulfide nanoparticles as a substrate using FTO glass slides. Moreover, the material characterization with respect to the morphology (scanning electron microscopy), phase composition (X-ray diffraction), crystallinity and molecular interactions (Raman spectroscopy) and electric (electrochemical performance) properties were provided. After annealing at 300 °C, smooth and well-adhered tin sulfide films were formed, consisting of smaller spherical particles 28–37 nm in size, and the thickness of annealed films is in the interval of 230–280 nm, depending on the number of tin sulfide synthesis cycles and the amount of complexing agent. According to Raman spectroscopy results, annealed films consist of SnS with secondary SnS2 or Sn2S3 phase. The obtained material was used for electrochemical calculations for supercapacitor application, and a significant increase of energetic values was seen after the annealing of films. The highest values of energetic parameters during this work have been provided by tin sulfide film synthesized with 1.0 g of L-ascorbic acid using 20 SILAR cycles.