As polyvinyl alcohol (PVA) hydrogels have shown a high potential as an ionic thermoelectric generator, this paper aims to study the thermoelectric (TE) power of salt-free PVA hydrogel. Ionic thermoelectric performance, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) are measured at different relative humidities. Findings show that salt-free PVA hydrogels can achieve a relatively high Seebeck (9.26 mV K−1) using only surrounding moisture. Hydrogels with low PVA content have a more stable TE output than hydrogels with high PVA content in high relative humidity conditions. Embedded Ni-foam-CNT electrodes stabilize performance, reduce noise, and provide superior capacitance, resistance, and thermoelectric performance over direct drop-casting of CNT on hydrogels. Recommended operating relative humidity (RH) ranges between 40 % and 60 %, while recommended PVA content ranges from 10 % to 15 % mass ratio of PVA in water. The results pave the way for using PVA hydrogels as thermoelectric devices in biocompatible applications.