The phase behaviors of ionic liquids (ILs) confined in nanospace and adsorbed on outer surface of nanoparticles are expected to be different from those of the bulk. Anomalous phase behaviors of room temperature ionic liquid tributylhexadecylphosphonium bromide (P₄₄₄₁₆Br) confined in ordered mesoporous silica nanoparticles with average pore size 3.7 nm and adsorbed on outer surface of the same silica nanoparticles were reported. It was revealed that the melting points (T(m)) of confined and adsorbed ILs depressed significantly in comparison with the bulk one. The T(m) depressions for confined and adsorbed ILs are 8 °C and 14 °C, respectively. For comparison with the phase behavior of confined P₄₄₄₁₆Br, 1-butyl-3-methylimidazolium bromide (BmimBr) was entrapped within silica nanopores, we observed an enhancement of 50 °C in T(m) under otherwise similar conditions. The XRD analysis indicates the formation of crystalline-like phase under confinement, in contrast to the amorphous phase in adsorbed IL. It was confirmed that the behavior of IL has clear difference. Moreover, the complex π-π stacking and H-bonding do not exist in the newly proposed phosphonium-based IL in comparison with the widely studied imidazolium-based IL. The opposite change in melting point of P₄₄₄₁₆Br@SiO₂ and BmimBr@SiO₂ indicates that the cationic species plays an important role in the variation of melting point.