A 3-D phase diagram of the HPC/H 2 O/ H 3 PO 4 tertiary system against various temperatures was established. Four distinct phases-the completely separated phase (S), the cloudy suspension phase (CS), the liquid crystalline miscible phase (LC), and the isotropically miscible phase (I)-were identified. The S phase shrank as the temperature increased, revealing that the HPC solubility increased with temperature, regardless of the LCST (lower critical solution temperature) characteristic. The addition of H 3 PO 4 suppressed the formation of LC phase. However, as the temperature was raised sharply from 50 to 70°C, the LC phase could only be maintained at high H 3 PO 4 concentration region; it was a triangular shape, and the top apex of the triangle was the temperature-invariant L* point (HPC/H 2 O/H 3 PO 4 38/9/53 wt%). The CS phase expanded considerably into the H 2 O-rich but H 3 PO 4 -poor region when the temperature continued to increase over 48°C. The LCST points of the CS phase that contained 0 and 15 wt% of H 3 PO 4 were 34 and 38°C, respectively. These CS results demonstrate that H 3 PO 4 suppresses the occurrence of LCST behavior. Additionally, the binodal curve exhibits a weak or even zero dependence of binodal temperature on the HPC concentration at HPC concentrations of less than 30 wt% in a pure water system. A hypothesis concerning the sequential desorption of water molecules was proposed to explain such behavior.