Efficient photoelectrocatalytic (PEC) water splitting could be the solution for environmental and energy problems by converting light energy into clean and renewable energy of H2. Here, we explored 2D palladium thiophosphate Pd3(PS4)2, which is a promising photocatalyst absorbing light in the visible range. We obtained a few-layer Pd3(PS4)2 through lithium-assisted exfoliation from the bulk phase and characterized it employing Raman spectroscopy, XPS, AFM, and STM combined with DFT calculations. The measured band gap for as-obtained few-layer Pd3(PS4)2 is 2.57 eV (indirect), and its band edges span the electrochemical potentials of the hydrogen and oxygen evolution reactions. The performance in the water-splitting reaction is studied under acidic, neutral, and alkaline conditions under violet irradiation at 420 nm. 2D palladium phosphochalcogenides semiconductor with bifunctional electrocatalytic and photoelectrocatalytic properties shows competitive performance compared with industrial Pt/C catalysts for solar-driven water splitting under acidic and alkaline conditions.