First evidence of hydrogen evolution by using titanium trisulphide (TiS₃) as a photoanode in a photoelectrochemical cell (PEC) is reported. Synthesized TiS₃, composed of numerous nanoribbons, has been structurally, morphologically and photoelectrochemically characterized. Moreover, the value of its flat band potential has been estimated (V_fb = −0.68 ± 0.05 V vs. Ag/AgCl) by Electrochemical Impedance Spectroscopy (EIS) measurements. This value has been used to depict the band energy levels of the TiS₃/electrolyte interface. Finally, flows of photogenerated hydrogen up to 1.80 ± 0.05 μmol H₂ min⁻¹ have been quantified by Mass Spectrometry (MS) at a (Ag/AgCl) bias potential of 0.3 V, yielding a photoconversion efficiency of about 7%.