The effects of a series of Hofmeister anions on the phase behaviors of a poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer were investigated with an automated melting point system. Well hydrated anions and poorly hydrated anions interacted with the polymer differently and further affected the phase transition of the polymer. Poorly hydrated anions worked through changing the interfacial tension at the polymer/aqueous interface and in enhancing the polymer hydration by ion binding. The phase transition of the polymer in the presence of well hydrated anions correlated directly to the hydration entropy of the anions. As a consequence, the polymer showed a two-step phase transition in solutions containing poorly hydrated anions while displayed a single-step phase transition in the presence of well hydrated anions. The mechanisms of how ions interact with the polymer and further modulate its phase behaviors were discussed.