Thermoelectric energy converters based on galvanic cells (TGC) offer the possibility of direct conversion of low-temperature waste heat into electrical energy and could therefore be a promising approach for an increase in the overall efficiency of energy conversion. Due to an externally applied heat source, a temperature gradient across the electrolyte is induced, leading to a gradient in the chemical potential of the species and an electrical potential difference between the electrodes. The aim of approaching an internal equilibrium state leads to various coupled molecular transport mechanisms taking place in the electrolyte, impacting the open circuit voltage (OCV) and the performance of the TGC. By applying the theory of non-equilibrium thermodynamics (NET) to describe these coupled processes, the interactions that occur can be characterized in more detail. In this work, a polymer electrolyte membrane (PEM)-based TGC with two H2/H2O electrodes of different temperatures and gas compositions is experimentally investigated. By controlling the gradients in temperature and concentration, different impacts on the resulting OCV can be identified. In addition, we present the measured coupling coefficient, representing the singular relation between the transport of the hydrogen ions inside the membrane and the electrical potential difference between the electrodes for a wide variety of working conditions.