The aim of this work was to carry out a photoelectrochemical process of hydrogen production and to examine the behavior of the SnS2 electrode in an aqueous solution of 1 and 3 mmol/dm^3 caffeic acid (CA) in 0.1 mol/dm3 NaCl in the presence or absence of 1 mmol/dm^3 ascorbic acid (AA). Measurements were performed for illuminated and non-illuminated electrodes, and the light source was an LED lamp. Electrochemical experiments were also carried out on a glassy carbon electrode (GC electrode) in order to determine the stability of CA and AA during illumination and to test the antioxidant properties of CA and AA against the O2.- radical. The methods used in this work for testing electrodes are cyclic voltammetry, linear polarization, electrochemical impedance spectroscopy and chronoamperometry. The results obtained using linear polarization and chronoamperometry methods indicate that the currents for the SnS2 electrode with the addition of sacrificial agent are much higher than without the presence of sacrificial agent, confirming the good activity of CA and AA. Also, the addition of sacrificial agents results in an increase in electrode stability. Investigations conducted on the GC electrode suggest that there was no photolysis of CA and AA when exposed to light, and AA is more effective as a sacrificial agent due to its lower potential value of the current peak. The increase in CA concentration and the addition of AA lead to an increase in antioxidant activity towards O2.- radicals. Impedance measurements show that illuminated SnS2 electrodes have much lower charge transfer resistances than non-illuminated ones, further confirming the good photoactivity of this electrode. The highest electrode stability and best photoactivity were achieved in a solution containing 1 mM CA and 1 mM AA, as confirmed by linear polarization and electrochemical impedance spectroscopy.