Thermo-responsive ionic compounds were synthesized to examine if they have a powerful ability to draw solutes for forward osmosis (FO). The investigated compounds were tetrabutylammonium benzenesulfonate, tetrabutylphosphonium benzenesulfonate, tetrabutylammonium 2-naphthalenesulfonate, and tetrabutylphosphonium 2-naphthalenesulfonate (abbreviated as [N₄₄₄₄][BS], [P₄₄₄₄][BS], [N₄₄₄₄][NS], and [P₄₄₄₄][NS]). The lower critical solution temperature (LCST) characteristics of the materials that formed the monocyclic aromatic compound [BS] were not confirmed; however, the LCSTs of others that formed the bicyclic aromatic compound [NS] were confirmed to be approximately 37 °C ([N₄₄₄₄][NS]) and 19 °C ([P₄₄₄₄][NS]) at 20 wt% in aqueous solutions; this is valued in reducing the energy required for recovery of the draw solute. In addition, it suggests that ammonium-based ionic compounds have a higher recovery temperature than phosphonium-based ionic compounds. When an active layer was oriented to a draw solution (AL-DS mode) and using 20 wt% aqueous [N₄₄₄₄][NS] draw solution at room temperature, water and reverse solute fluxes were about 3.07 LMH and 0.58 gMH, respectively. Thus, this is the first study to investigate structural transformations of the anion and central atom of the cation and to examine prospective draw solutes of the FO system in this series.