Harvesting energy from the environment to power the self-sustained systems has long been desired1,2. Ionic thermoelectric (i-TE) material with mobile ions as charge carriers has the advantage to generate large thermal voltages at low operating temperatures3-5. Recent works improved the thermopower substantially by modifying the polymer matrix of the i-TE hydrogels6-9. But the mobile ions have not been systematically studied in the context of i-TE hydrogels. This study highlights the role of ions in i-TE hydrogels employing a polyvinyl alcohol (PVA) polymer matrix and a number of ion providers, e.g. KOH, KNO3, KCl, KBr, NaI, KI, and CsI. The relationship between the intrinsic physical parameters of the ion and the thermoelectric performance is established, indicating electronegativity of the cation and the ability to influence the hydrogen bond by the anion are two crucial factors. Among these i-TE hydrogels, PVA/CsI hydrogel exhibits the largest ionic Seebeck coefficient, reaching 52.9 mV K-1, which is the greatest of all i-TE materials reported till date. In addition, PVA/NaI hydrogel exhibits excellent TE properties, with a record ZT value of 5.09 at room temperature. This flexible, inexpensive hydrogel that compatible with large-scale manufacturing shows great promise for low-grade thermal energy harvesting.