The thermal-responsive polymers, poly(alkane-1,#-diylbis(tri-n-butylphosphonium) 4-vinylbenzenesulfonate) (PSSBP#, # = 8, 6, and 4), where # is the number of carbon atoms in the central bridge structure of the dicationic phosphonium moiety, were synthesized to examine their potential application as draw solutes in forward osmosis (FO). The polymers exhibited low critical solution temperature (LCST) characteristics in aqueous solutions, which is essential for recovering a draw solute from pure water. The LCSTs of the 20 wt% aqueous solutions of PSSBP8, PSSBP6, and PSSBP4 were confirmed to be approximately 30, 38, and 26 °C, respectively, which is advantageous in terms of energy requirements for the recovering draw solute. When the concentration of the PSSBP4 draw solution was 20 wt%, water flux and reverse solute flux were approximately 1.61 LMH and 0.91 gMH, respectively, in the active layer facing the draw solution (AL-DS) system when the feed solution was distilled water. The PSSBP# thermal-responsive draw solute has considerable potential for use as a next-generation draw solute because of its excellent osmotic performance and efficient recovery. Therefore, this study provides inspiration for novel ideas regarding structural transformations of polymers and their applicability as draw solutes.